NL1007470C2 - Benzotriazole UV absorbers with improved durability. - Google Patents

Description

Benzotriazole UV absorbers with improved durability

Benzotriazole UV absorbers, which are substituted in the benzo ring with electron withdrawing groups, exhibit improved durability and low loss rates when incorporated into automotive coatings.

The benzotriazoles have long been an important class of UV absorbers and have gained great commercial importance and acceptance for many industrial applications. The prior art is full of references for its preparation and applicability. However, as the requirements become even stricter and more demanding, the search for even more stable and durable benzotriazoles continues. The gradual phasing out of HAPS solvents, such as xylene, due to environmental concerns and their replacement with non-HAPS solvents, such as esters, ethers or ketones, and the increased durability requirements for automotive paints make this search more urgent. Indeed, the automotive industry is extremely concerned with UVA losses from car paints and paints, as the publication of J.L. Gerlock et al., Proc. 36th Annual Tech. Sym. (Cleveland Coating Society) May 18, 20 1993 -

Vysokomol Soedin, Ser. A, 1 ^ (3). 553 (1976) describes the linear dependence of hydrogen bond strength and photostability in benzotriazoles.

J.E. Pickett et al., Angew. Makromol. Chem. 232, 229 (1995) discloses the degradation of benzotriazole UV absorbers in poly (methyl methacrylate) films under the influence of light. Structural variation generally caused only minor differences in degradation rates unless the substitution disrupts intramolecular hydrogen bonds critical for stability. Pickett et al. Have not tested benzotriazoles containing both electron withdrawing and electron donor groups, as in the present invention.

The prior art concludes that enhancing the hydrogen bond leads to a more stable benzotriazole, but does not teach how to accomplish this. The present invention discloses benzotriazoles that exhibit improved durability, but surprisingly, this increased durability is not always related to greater hydrogen bond strength. Compounds with improved durability often have 1 0 0 7 47 0 2 weaker and no stronger hydrogen bonds.

In U.S. Patent Nos. 4226763; 4278589; 4315848; 4279009; 4347180; 555476Ο; 5,563,242; 5574166 and 5607907 disclose selected benzotriazoles substituted in the 3-position of the hydroxy-5 phenyl ring with an α-cumyl group, which exhibit very good durability in car paints. These benzotriazoles represent the current state of the art. The present invention is directed to the preparation of benzotriazoles which exhibit even better durability and low loss rates than the prior art benzotriazoles.

In U.S. Patents 5,278,314; 5,280,129; 5436349 and 5516914 disclose red-shifted benzotriazoles. These benzotriazoles are substituted at the 5 "site of the benzo ring with thioethers, alkylsulfonyl or phenylsulfonyl groups. Red shifting of the benzotriazoles is desirable for spectral reasons. A group in the 5 "position which is also electron-withdrawing provides additional advantages of low loss rates and durability, as found in the present invention.

The present invention relates to benzotriazole UV-20 absorbers with improved stability and durability and a low loss rate when incorporated into automotive paints.

More particularly, the present invention relates to a lacquer composition stabilized with a benzotriazole, which benzotriazole exhibits improved durability and a low loss rate when incorporated into the lacquer, which composition consists of (a) a resin selected from the group of a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane-modified acrylic melamine, an acrylic resin with carbamate side groups cross-linked with melamine, or an acrylic polyol resin, which is cross-linked with carbamate groups containing melamine, and

(b) 0.01-5 wt%, based on solid resin particles, of a benzotriazole of the formula A, B, C or D

1007470 3

OH

5 χτ> -α, A) r2 10

OH

T L Rj J 2 20 ΓG '° \ 1 \ ± / (C) G2 CH2CH2CO - Rs 25 n 30 G, OH OH / G' ^ y = <K JL _Jl

Gj ^ o <W / N °! r2 R2 35 where é U ü 7 4 7 0 4

Gj, G2 or T is an electron withdrawing group,

Gj is hydrogen or halogen, G2 is halogen, nitro, cyano, R3S0-, R3S02-, -C00G3, CF3 ~, -P (0) (C6H5) 2, -CO-G3, -CO-nh-g3, -co- n (g3) 2, -n (g3) -co-g3, 5 CO-IG, CO-1-G3 / r /

-N -N

\\ CO-J is co-1 10, G 3 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 1 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl , or where the phenyl group or phenylalkyl group on the phenyl ring is substituted with 1-4 alkyl groups of 1-4 carbon atoms,

Rj is hydrogen, straight or branched chain alkyl of 1-24 carbon atoms, straight or branched chain alkenyl of 2-18 carbon atoms, cycloalkyl of 5-12 carbon atoms, phenylalkyl of 7-15 carbon atoms, phenyl, or where the phenyl group or phenylalkyl group is on the phenyl ring is substituted with 1-4 alkyl groups with 1-4 carbon atoms, R2 straight or branched alkyl with 1-24 carbon atoms, straight or branched alkenyl with 2-18 carbon atoms, cycloalkyl with ^ -12 carbon atoms, phenylalkyl with 7-15 carbon atoms is phenyl, or wherein the phenyl group or phenylalkyl group on the phenyl ring is substituted with 1-4 alkyl groups of 1-4 carbon atoms; or R 2 is hydroxyl or -OR 4, wherein R / is straight or branched chain alkyl of 1-24 carbon atoms; or wherein the alkyl group is substituted with one or more groups -OH, -OCO-R 1, -O-R 1, -NCO, or -NH 2 or mixtures thereof; or wherein the alkyl-30 group or the alkenyl group are interrupted by one or more groups -O-, -NH- or -NRU- or mixtures thereof and which may be unsubstituted or substituted with one or more of the groups -OH, -OR /, or —NH2 or mixtures thereof; or R2 -SR · ,. -NHR3 or -N (R3) 2; or R2 is - (CH2) ', -CO-X- (Z) p -Y-R] 5, wherein X is -O- or -N (Rh,) -.

Y is -O- or —N (R, 7) -.

Z is C2-C12 alkylene or C / -C12 alkylene interrupted by t 0 7 7 4 7 0 5 to three nitrogen atoms, oxygen atoms or a mixture thereof, or is C3-C12 alkylene, butenylene, butynylene, cyclohexylene or phenylene , each of which is substituted with a hydroxyl group, m is zero, 1 or 2, 5 is p 1, or p is also zero if X and Y are —N (R 1 £ 1) - and -N (R 17) -, R 15 a group -C0-C (Rg) = C (H) R19, or when Y is -N (R17) - together with R17 forms a group -C0-CH = CH-CO-, wherein Rlg is hydrogen or methyl and R19 is hydrogen, methyl or -CO-X-R20, wherein R20 is hydrogen, C3-C12alkyl 10 or a group of the formula

OH

^ = ^ (CHa) is "CO - X - (Z) -, in which the symbols R ,, R ,, X, Z, m and p have the meanings defined above and R; t, and R, T independently of each other is hydrogen, C 1 -C 12 alkyl, C 3 -C 12 alkyl interrupted by 1-3 oxygen atoms or cyclohexyl or C7-C 12 aralkyl and R 16 together with R 1 in case Z is ethylene also forms ethylene, n 1 or Is 2, when n is 1, R is Cl, OR ,, or NR-, Rg or R; —PO (OR (2) 2, —OSi (R;.) 3 or -CO2 -Rn, or straight or branched C1 -C12 alkyl, interrupted by -O-, -S-, or -NRn, and which may be unsubstituted or substituted with -OH or -OCO-R 1, C 3 -C 12 cycloalkyl, which is unsubstituted or substituted with -OH straight or branched C 2 -C 18 alkenyl, which is unsubstituted or substituted is with -OH, C7 -C13 aralkyl, -CH2-CHOH-R13 or glycidyl, R6 is hydrogen, straight or branched C1 -C1 alkyl, which is unsubstituted or substituted with one or more groups OH, OR /, or NH2 , is, or 35 is -0Rfc - (0CH2CH2) W0H or - (0CH2CH2) w0R21, where w is 1-12 and R23 is alkyl of 1-12 carbon atoms, R? and R8 is independently hydrogen, alkyl of 1-18 carbon atoms, straight or branched C3 -C18 alkyl interrupted by -O-, -S- or 1 0 7 7 4 7 0 6 -NRn-, C5 -C12 cycloalkyl, C6 -C39 aryl or C1 -C3 hydroxyalkyl, or R ? and R8 together with the N atom are a pyrrolidine, piperidine, piperazine or morpholination, when η is 2, R5 is one of the divalent groups -O-Rg-O- or 5 -N (Rn) -R10-N (R11) - is R9 C2-Cgalkylene, C 1 -Cg alkenylene, 0 / - alkynylene, cyclohexylene, straight or branched C (C 1 -C 10 alkylene, which is interrupted by -O- or by —CH 2 —CH 2 H-CH 2 —O-R 19 O — CH 2 —CH 2 H-CH 2 -, R 10 is straight or branched C 2 -C 12 alkylene, which may 10 are interrupted by -0-, cyclohexylene or 15 - (^ y1 — C ΗΓ - \ / - 20 or R1C, and Rn with the two nitrogen atoms form a piperazine ring,

R 4 straight or branched C 2 -C 6 alkylene or straight or branched C 1 -C 6 C, alkylene interrupted by -O-, cycloalkylene, arylene or 25 _ CH 3 _____ ch 3 30 CH 3 _ 35 CH 3, wherein R 7 and R 8 are independently hydrogen or alkyl with 1 -1 S carbon atoms are whether R7 and R8 together are alkylene of 4-6 carbon atoms, 3-oxapentamethylene, 3 "in-inopentamethylene or 3-methyliminopenta-1 O 7 47 0 7 methylene,

R n is hydrogen, straight or branched C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl, straight or branched C 3 -C 8 alkenyl, C 8 -C 14 aryl or C 7 -C 15 aralkyl, R 12 straight or branched C 1 -C 18 alkyl, straight or branched C3- C 1-8 alkenyl, C 5 -C 10 cycloalkyl, C 6 -C 18 aryl or C 7 -C 15 aralkyl, R 13 is H, straight or branched C 1 -C 18 alkyl, which is substituted with -P0 (0R12) 2, phenyl, which is unsubstituted or is substituted with OH, C7 "is C15 aralkyl or -CH20R12, R3 is alkyl of 1-20 carbon atoms, hydroxyalkyl of 2-20 carbon-10 atoms, alkenyl of 3" -18 carbon atoms, cycloalkyl of ^ -12 carbon atoms, phenylalkyl of 7 ~ 15 carbon atoms, aryl of 6-10 carbon atoms or where the aryl is substituted with one or two alkyl groups of 1-4 carbon atoms, or 1,1,2,2-tetrahydroperfluoroalkyl, the perfluoroalkyl group having 6-16 carbon atoms has, 15 L is alkylene of 1-12 carbon atoms, alkylidene of 2-12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene and T is -so-, -so2-, -so-e-so-, -so2- e-so2-, -co-, -co -e-co-, -C00-E-0C0-, -CO-NG -E-NG-CO- or -NG - CO-E-CO-NG - where E is alkylene with 2-12 carbon atoms, cycloalkylene with 5 "20 12 carbon atoms or alkylene, interrupted or terminated by cyclohexylene with 8-12 carbon atoms, which benzotriazole exhibits improved durability and low loss rate values when the lacquer is exposed to actinic radiation, as shown by a loss of less than 0.22 absorbent units after exposure for 1200 hours or less than 0.27 absorbent units after exposure for 1500 hours or less than 0.40 absorbent units after exposure for 2500 hours in a Xenon Arc Weather-OMeter.

Preferably component (b) is a compound of the formula A '30

OH

GN (A) R2 1 0 0 7 47 0 8 wherein G2 is fluoro, chloro, cyano, R3S02-, CF3 ~, -CO — G3, -C00 ~ G3 or —CO — N (G3) 2, G3 alkyl with 1 -12 carbon atoms, 5 R 1 is hydrogen, alkyl of 1-12 carbon atoms, phenyl or phenylalkyl of 7-15 carbon atoms, or phenyl or phenylalkyl substituted on the phenyl ring with 1 or 2 alkyl groups of 1 to 4 carbon atoms, R2 alkyl of 1-12 carbon atoms, phenyl, phenylalkyl of 7-15 carbon atoms or -CH2CH2C00Gi where G4 is hydrogen or alkyl of 1-1024 carbon atoms or where the alkyl group is substituted with OH is interrupted by one to six -0- atoms or both is substituted with OH and interrupted by one to -O atoms, and

R 1 is alkyl of 1-1δ carbon atoms or aryl of 6-10 carbon atoms or wherein the aryl group is substituted with one or two alkyl-15 groups of 1-4 carbon atoms.

Most preferably in the compound of formula A 'G2 is fluorine, chlorine, cyano, R, SO2-, CF-, -C00-G, or -C0-N (G,) ,,

Gj alkyl of 1-8 carbon atoms,

R 1 is hydrogen, phenyl or α-cumyl, R 2 is alkyl of 4-12 carbon atoms or phenyl, and R 3 is phenyl or alkyl of 8-12 carbon atoms.

Particular preference is given to the compounds of the formula A 'wherein G2 is phenyl-SO2-, octyl-SO2-, fluoro or CF-, R3 is α-cumyl or phenyl and R2 is tert-butyl or tert-octyl.

Preferably, the resin is a thermosetting acrylic melamine resin or an acrylic urethane resin.

Examples of the different groups are the following:

When one of the groups R3 to R21 is alkyl, such groups are, for example, methyl, ethyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl, 2-ethylhexyl, tert-octyl, lauryl, tert-dodecyl, tridecyl, n-hexadecyl, n-octadecyl and eicosyl; if one of the groups is alkenyl, such a group is, for example, allyl or oleyl; when one of the groups is cycloalkyl, such groups are, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl; when one of the groups is phenylalkyl, such groups are, for example, benzyl, phenethyl, α-methylbenzyl and α-α-dimethyl-benzyl; and when one of the groups is aryl, these groups are, for example, phenyl, naphthyl, or when substituted with alkyl they are, for example, tolyl and xylyl. When R6 is alkyl substituted with one or more -O- groups and / or substituted with one or more -OH groups, the -0R6 group may be - (0CH2CH2) w0H or - (0CH2CH2) w0R21, w 1- 12 and R21 is alkyl of 1-12 carbon atoms.

When E is alkylene, it is, for example, ethylene, tetramethylene, hexamethylene, 2-methyl-1,4-tetramethylene, hexamethylene, octamethylene, decamethylene and dodecamethylene; when E is cycloalkylene, it is, for example, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and cyclododecylene; and when E is alkylene interrupted by or terminated with cyclohexylene, it is, for example, the saturated diyl group obtained from limonene which is referred to herein as dihydrolimonene diyl.

A further preferred embodiment of the invention is a compound of formula III, wherein R is tert-butyl, η is 1, R-15 is phenyl and R 3 is -ORt, wherein R 6 is a straight or substituted octyl group. Yet another preferred embodiment of the present invention is a compound of formula C wherein n is 2, R 1 is tert-butyl, R 3 is phenyl, and R is -O-R 1 -O-, wherein R 1 is? C2 -C2L is alkylene interrupted by -O- or by -CH2-CHOH-CH2-O-R: -O-CH2-CHOH-CH2-. When E is alkylene, it is, for example, ethylene, tetramethylene, hexamethylene, 2-methyl-1,1-tetramethylene, hexamethylene, octamethylene, decamethylene and dodecamethylene; when E is cycloalkylene, it is, for example, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and cyclododecylene; and when E is alkylene interrupted by or terminated with cyclohexylene, it is, for example, the saturated diyl group obtained from limonene, which is referred to herein as dihydrolimonene diyl.

When the present compounds contain a free carboxyl group, wherein R 2 is -CH 2 CH 2 CO 2 Rt, where Rfc is hydrogen, the alkali metal or amine salts of such acids are also considered part of this invention, thereby making such UV absorbers due to the improved solubility in water of such present compounds can be used in aqueous systems.

R6, R- and Rg may be the following C3 -C18 alkyl groups interrupted by -O-, -S- or -NRn- or may be substituted with OH: methoxyethyl, ethoxyethyl, butoxyethyl, butoxypropyl, methylthioethyl, CH30CH2CH20CH2CH2-, CH3CH20CH2CH20CH2CH--, C18H90CH2CH20CH2CH2-, ethylthiopropyl, octylthiopropyl, dodecyloxypropyl, 2-hydroxyethyl, 2- 1007470-hydroxypropyl, ^ -hydroxybutyl, 6-hydroxyhexyl, -CH2CH2-NH2 -NH2 -CH2-NH2-NH2 (CH 2) -CH 2 CH (C 2 H-R 6, R 7, R 5, R 11 and R 12 may be the following C 8 -C 12 cycloalkyl groups: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclo-dodecyl. In the case of R 6, the group may also be substituted with -OH.

R7, Rg, and Rn may be the following alkenyl groups: allyl, methallyl, 2-n-hexenyl or--n-octenyl.

When Rg is alkenyl it can have the same meaning as R7, Rg and 10 Rn as alkenyl groups, but it can also be -CH = CH2, n-undec-10-enyl or n-octadec-9-enyl and it is also possible that the group Rg is substituted with -OH.

R7 and Rg may be the following C 1 -C 15 aralkyl groups: benzyl, α-phenethyl, 2-phenethyl or A-tert-butyl benzyl.

When Rnm R 13 or R 12 are aralkyl, they can independently have the same meaning as R- or Rg.

Independently of each other, R, Rg and R :) can be the following Ct.-C, aryl groups: phenyl, α-naphthyl or β-naphthyl.

When R- and Rg are C 1 -C-hydroxyalkyl, they may be the following groups: hydroxymethyl, 2-hydroxyethyl or 2-hydroxypropyl.

R9 and R19 can be the following C2-C8 alkylene groups: ethylene, propylene, butylene, hexylene or octylene.

R10 may be the same alkylene groups, but in addition may also be a higher molecular weight group such as decylene or dodecylene.

When Rq is a C4-Ce alkenylene group, the following is an example of a suitable group: butenylene.

In the case of R9 and R1 / f, suitable straight or branched alkyl groups interrupted by -O- are the following groups: -CH2CH20CH2CH2-, -CH (CH3) -CH2-0-CH2-CH (CH3) -, -CH2CH20CH2CH20CH2CH; - and -CH-.CH20CH2CH20CH2CH20CH2CH2-.

When R1Z1 is a cycloalkylene group, it includes the following groups: 1,3-cyclohexylene and 1,1A-cyclohexylene.

When Ri is arylene, it may especially be the following groups: 1,3 "phenylene or 1,4-phenylene.

Z is a straight or branched C 2 -C 12 alkylene group. Z is, for example, ethylene, propylene, tetramethylene, hexamethylene, octamethylene, dodecamethylene, 1,1-ethylidene, 2,2-propylidene, 2,2-amyl-1 µU 7 4 7 0 11 idene or 2-ethylhexamethylene. C2-Ct) alkylene groups are preferred.

For example, if Z is oxygen-interrupted C 1 -C 12 alkylene, it is, for example: -ch2-ch2-o-ch2-ch2-, -CH2-CH2-0-CH2-CH2-CH2,5 CH2-CH2-0-CH2-CH2 -O-CH2-CH2 or -CH2-CH2-0-CH2-CH2-0-CH2-CH2-0-CH2-CH2- and when alkylene is interrupted by nitrogen it is meant a group -N (Ri6) -, where Rfc defined above, for example -CH2 -CH2-NH-CH2-CH2-CH2-CH2, -CH2-CH2-CH2-NH— (CH2) g- or -CH2CH2-CH2-N (CH - CH2-CH (c2h5 ) (CH2) u-.

Z as a C3-C12 alkylene group substituted with a hydroxyl group is 2-hydroxytetramethylene, 2-hydroxyhexamethylene and in particular 2-hydroxytrimethylene.

As cyclohexylene, Z is, for example, 1,4-cyclohexylene and especially 1,2-cyclohexylene.

As phenylene, Z is, for example, m-phenylene or p-phenylene.

m can be zero, 1 or 2, but is preferably 2.

p is preferably 1, but can also be zero if both X and Y are bonded by nitrogen.

As C 1 -C 8 alkyl, R is, for example: methyl, ethyl, n-propyl, iso-20 propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-amyl, n-hexyl, n-heptvl , n-octyl, 2-ethylhexyl or tert-octyl. Tert-butyl is preferred.

As C-C12 alkyl can R1Ê, R1? and R2C have the same meaning as above in R, and further they may be straight or branched nonyl, decyl, undecyl or dodecyl.

When R; t and R; - are oxygen-interrupted alkyl groups, the examples are the same as those described above at Z.

Examples of R: t and R17 as aralkyl are: benzyl, α-methylbenzyl, 1-phenylethyl, α, α-dimethylbenzyl or 1-phenyipropyl.

When Z is ethylene, Rf. and R1? together also form ethylene, which is equivalent to a bridging by means of a piperazine group.

If Y is a group -N (R17) - R15 and R17 together form a group -CO — CH = CH-C0- and thus form the substituent., Mi 470 12 _Λ γ ο 10 on the group -Χ- (Ζ ) ρ-.

However, the preferred meaning of R 15 is -CO-C (R 11) = CHR 1; j, where R 11 and R 19 are preferably methyl and especially hydrogen.

R2 is -CH2-CH2-CO-O-C (G) = CH2 and G is hydrogen or methyl.

The present invention also relates to new benzotriazoles of formulas I. II, III or IV

OH

G. I_, / E, I Ln // “

Gj N N--

Ez 25

OH

(^ ynv _H <'30 TLE; 2 Ί ü 0 7 4 7 0 13 - G 0H - 5 i ^ S <> VnT = N // ΧΧ> - (Λ »G2] CHjCHjCO-j-Eg n 10 G, OH OH / 6, 15 Jvl-A- / n I / I (IN) G * ι ^ γ g * in which 20 G is hydrogen or halogen, 0-cyano, E, S0-, E3S0; -C00G, , CF ^ -, -P (O) (C6H -); ,, -C0-G ,, -C0-NHG, or -C0-N (G3) 2, G is straight or branched chain alkyl of 1-24 carbon atoms straight or branched chain alkenyl of 2-18 carbon atoms, cycloalkyl of 5 ~ 12 carbon-25 atoms, phenylalkyl of 7-15 carbon atoms, phenyl, or where the phenyl group or phenylalkyl group on the phenyl ring is substituted with 1-4 alkyl groups of 1 -4 carbon atoms, E; hydrogen, phenylalkyl of 7-15 carbon atoms or phenyl, or wherein the phenyl group or phenylalkyl group is substituted on the phenyl ring with 1-4 alkyl groups of 1-4 carbon atoms, E2 straight or branched alkyl with 1-24 carbon atoms, straight or branched alkenyl with 2 -18 carbon atoms, cycloalkyl with 5-12 carbon atoms, phenylalkyl with 7-15 carbon atoms, phenyl, or where the phenyl group or the phenylalkyl group on the phenyl ring is substituted with 1-3 alkyl groups with 1-4 carbon atoms; or E2 is hydroxyl or -0E2, wherein E1 is straight or branched chain alkyl of 1-24 carbon atoms; or wherein the alkyl group is substituted with one or more groups -OH, -OCO-En, -OEi, -NCO or -NH 2 or mixtures thereof; or wherein the alkyl- 1007470-14 group or the alkenyl group are interrupted by one or more groups -O-, —NH- or —NE4— or mixtures thereof and which may be unsubstituted or substituted with one or more of the groups -OH -0E4 or -NH2 or mixtures thereof; or E2 is -SE · -1 -NHE3 or -N (E3) 2; or E-5 - (CH2) - —CO-X- (Z) p — Y-Ej 5, wherein X is -0- or -N (Eiè) -, Y is -0- or -N (E1T) - Z is C2 -C12 alkylene or C4 -C12alkylene interrupted by one to three nitrogen atoms, oxygen atoms or a mixture thereof, or C3 -C12 alkylene, butenylene, butynylene, cyclohexylene or phenylene, each of which is substituted with a hydroxyl group, m is zero, 1 or 2, p is 1, or p is also zero if X and Y are -N (Ei (J- and 15 -N (E1T) -, respectively),

Ej5 is a group -CO-C (E36) = C (H) E, 9, or when Y —N (E; 7) - is together with E1T forms a group —CO — CH = CH-CO-, wherein Elg hydrogen or methyl and E19 is hydrogen, methyl or -C0-X-E2r. wherein E 20 is hydrogen, C 1 -C 12 alkyl or a group of the formula 20

OH

G, _ \ _, / R · rry-fë 25 \ = A (chs) -oo-x-fflp-, where the symbols E :, G2, X, Z, m and p have the meanings defined above and Elè and E17 is independently hydrogen, C 1 -C 12 alkyl, C 3 -C 12 alkyl interrupted by 1-3 oxygen atoms or cyclohexyl or C7-C15 aralkyl and Eu, together with E1T in case Z is ethylene, also ethylene forms, η is 1 or 2, if η is 1. E3 is Cl, 0Eb or NE7Ee or is 35 E5 -P0 (0Ei2) 2, -0Si (En) 3 or -0C0-E 4, or straight or branched C 1 -C 2 alkyl, interrupted by -0-, -S -or ~ NEn and which may be unsubstituted or substituted with -OH or -OCO-En, C 1 -C 12 cycloalkyl, which is unsubstituted or substituted 1 0 7 7 7 15 by -OH, straight or branched C 2 -C 18 alkenyl which is unsubstituted or substituted with -OH, C 7 -C 15 aralkyl, -CH 2 -CHOH-E; -or glycidyl,

Eg is hydrogen, straight or branched C 1 -C 20 alkyl, which is unsubstituted or substituted with one or more groups OH, OE 4, or NH 2, or —OEg, is - (0CH2CH2.) WOH or - (0CH2CH2) wOE21 where w is 1-12 and E2i is alkyl of 1-12 carbon atoms, E? and Efc is independently hydrogen, alkyl of 1-18 carbon atoms, straight or branched C 1 -C 18 alkyl interrupted by -O-, -S- or 10-NEjj -, C-C 12 cycloalkyl, C 8 -C 18 aryl, or Cj-Cj are hydroxyalkyl, or E ~ and E6 together with the N atom are a pyrrolidine, piperidine, piperazine or morpholination, when η is 2, E.- one of the divalent groups -OE ^ -O- or -h (Ej;) -E; o-N (E: Y) - is.

15 Eg C 2 -C 8 alkylene, Cq-C 8 alkenylene, C 1 -alkynylene, cyclohexylene, straight or branched C 1 -C 3 alkylene interrupted by -O- or thaw -CH 2 -CHOH-CHt-0-Ei 10- CH.-CHOH-CHy-, E1C is straight or branched C1 -C12 alkylene, which may be interrupted by -O-, cyclohexylene or 20 or E10 and E, j with the two nitrogen atoms forming a piperazine ring, E · straight or branched C 1 -C 8 alkylene or straight or branched C 1 -C 8; alkylene interrupted by -0-, cycloalkylene, arylene or iu u) is 47 0 16 -ofo- <5 CH 3 ch 3 10, where E? and Eg are independently hydrogen or alkyl of 1 -13 carbon atoms or E- and Eg together are alkylene of 4-6 carbon atoms, 3-15 oxapentamethylene, 3-imin-PentaiDethylene or 3- [nethyliinopenta-methylene,

And hydrogen is straight or branched C 1 -C 6 alkyl, C-C 2 cycloalkyl, straight or branched C 3 -C 8 alkenyl, C 6 -C, aryl or C-C aralkyl, E 12 straight or branched C 1 -C 5 alkyl, straight or branched C 1 -C 1); alkenyl, C5 -C10 cycloalkyl, C6 -C16 aryl or C7 -C15 aralkyl, E13 is H, straight or branched C 1 -C 6 alkyl, which is substituted with -P0 (0E12) 2, phenyl, which is or is unsubstituted substituted with OH, C7-C15 is aralkyl or -CH20E12, E3 alkyl of 1-20 carbon atoms, hydroxyalkyl of 2-20 carbon-25 atoms, alkenyl of 3 "1δ carbon atoms, cycloalkyl of 5 ~ 12 carbon atoms, phenylalkyl of 7-15 carbon atoms, aryl of 6-10 carbon atoms or wherein the aryl is substituted with one or two alkyl groups of 1-4 carbon atoms, or 1,1,2,2-tetrahydroperfluoroalkyl, where the perfluoroalkyl group has 6-16 carbon atoms, 30 L alkylene with 1-12 carbon atoms, alkylidene with 2-12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and T is -SO-. —S02—, -S0-E-S0-, -S02-E-S02-, —CO—, -C0-E-C0-, -C00-E-0C0- or -C0-NGj-E-NG-— Is CO-, where E is alkylene of 2-12 carbon atoms, cycloalkylene of 5 ~ 35 12 carbon atoms or alkylene interrupted or terminated by cyclohexylene of 8-12 carbon atoms, is G-G3 or hydrogen and, of course, that Ej is not phenylalkyl when G2 is E3S0- or 10 0 7 47 0 17 E3SO2.

Preferably the new benzotriazole is a compound of the formula I '

5 OH

\ - (I)

ίο I

E2 where G2 is cyan. E3S02-, CF, -. -COr-G3, -C0-NHG3 or -C0-N (G.) =.

15 Gj alkyl of 1-12 carbon atoms,

Ej is hydrogen, phenyl or phenylalkyl of 7-15 carbon atoms, or the phenyl group or phenylalkyl group on the phenyl ring is substituted with 1 or 2 alkyl groups of 1-4 carbon atoms, E2 alkyl of 1-12 carbon atoms, phenyl, phenylalkyl of 7 ~ 15 20 is carbon or -CH2CH2C00Gi, where G ^ is hydrogen or alkyl of 1-

Is 24 carbon atoms, the alkyl group being substituted with OH

or is interrupted by one to six -0 atoms or is both substituted with OH and interrupted by one to six -0 atoms.

E3 alkyl of 8-18 carbon atoms or aryl of 6-10 carbon atoms is 25, or wherein the aryl group is substituted with one or two alkyl groups of 1-4 carbon atoms with the proviso that E: is not phenylalkyl as G2 E, SO- or EjSOy-.

Most preferably, in the compound of formula I ', 30 G 2 is cyano. E3S02-, CF-, -C0-G3 or -C0-N (G3) 2, G3 alkyl of 1-8 carbon atoms,

Ej is hydrogen, phenyl or α-cumyl, E2 alkyl of 4-12 carbon atoms and E3 is phenyl or actyl, and with the proviso that Wj is not α-cumyl when G2 is E3SO2-.

Particular preference is given to the compounds of the formula I ', wherein G2 is CF3-, E: α-cumyl and E2 is tert-butyl or tert-octyl.

U 0 7 4 7 0 18

The present invention also relates to a composition stabilized against thermal, oxidative or light-induced degradation, which consists of (a) an organic material subject to thermal, oxidative or light-induced degradation and (b) an effective stabilizing amount of a compound of the formula I, II, III or IV.

Preferably, the organic material is a natural, semi-synthetic or synthetic polymer, in particular a thermoplastic polymer.

Most preferably, the polymer is a polyolefin or polycarbonate, especially polyethylene or polypropylene; most particularly polypropylene.

In another preferred embodiment of the present invention, the organic material is a resin selected from the group of a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane-modified acrylic melamine, an acrylic resin with carbamate side groups. which is cross-linked with melamine, or an acrylic polyol resin, which is cross-linked with melamine-containing carbamate groups.

Most preferably, the resin is a thermosetting acrylic melamine resin or an acrylic urethane resin.

In yet another preferred embodiment of the present invention, the organic material is a recording material.

The recording materials of the invention are suitable for pressure sensitive copying systems, photocopying systems using microcapsules, for heat sensitive copying systems, photographic materials and inkjet printing.

The recording materials according to the invention can be distinguished by an unexpected improvement in quality, in particular with regard to color fastness to light.

The recording materials according to the invention have the construction known for the respective application. They consist of a conventional carrier, for example paper or a plastic film, which is coated with one or more layers. Depending on the type of material, these layers contain the appropriate necessary components, in the case of photographic materials, for example, silver halide emulsions, dye couplers. dyes and the like.

1 ü U 7 4 7 0 19

Material particularly suitable for inkjet printing has a layer, which is particularly absorbent to ink, on a conventional support. Uncoated paper can also be used for inkjet printing. In this case, the paper serves as the carrier material and the ink absorbing layer at the same time. Suitable material for inkjet printing is described, for example, in U.S. Patent No. 5073 ^ 8 (to be incorporated herein by reference).

The recording material may also be transparent, such as, for example, in the case of projection films.

The compounds of the formula I, II, III or IV can already be included in papermaking during the production of carding material, for example by adding it to the paper pulp. A second method of application is spraying the carding material with an aqueous solution of compounds of the formula I, II, III or IV or by the compounds of the formula I. II. Ill or IV to add to the coating composition.

Coating compositions intended for transparent recording materials suitable for projection cannot contain particles that scatter light, such as pigments and fillers.

The dye-binding coating composition can contain a number of other additives, such as, for example, antioxidants. light stabilizers (including UV absorbers not belonging to the UV absorbers according to the invention), viscosity improvers, fluorescent bleaches, biocides and / or antistatic agents.

The coating composition is usually prepared as follows: the water-soluble components, for example the binder, are dissolved in water and stirred together. The solid components, for example fillers and other additives already described, are dispersed in this aqueous medium. The dispersion is advantageously carried out with the aid of devices, for example ultrasonic samples, turbine stirrers, homogenizers, colloid mills, ball mills, sand mills, high speed stirrers and the like. The compounds of the formula I, II, III and IV can be easily incorporated into the coating composition.

The recording material of this invention preferably contains 1 to 5000 mg / m2, especially 50-1200 mg / m2, of a compound of the formula I.

As already mentioned, the recording materials according to the invention cover a wide range. For example, the compounds of formula 1, 11, III or IV can be used in pressure-sensitive copy systems. They can be added either to the paper to protect the microencapsulated dye precursors there from light or to the binder of the developer layer to protect the dyes formed therein.

Photocopying systems using photosensitive microcapsules 10 which are developed by pressure are described in U.S. Patents 4,416,966; 4483912; 4352200; 4535050; 45365463; 4551407; 4562137 and 4608330, and also in EP-A-139479; EP-A-162664; ep-a-164931; EP-A-237024; EP-A-237025 or ep-A-26OI29. In all these systems, the compounds can be introduced into the dye-receiving layer. However, the compounds can also be introduced into the donor layer to protect the color formers from light.

Photographic materials that can be stabilized are photographic dyes and layers containing such dyes or their precursors, for example, photographic paper and films. Suitable materials are described, for example, in U.S. Patent 5,364,749 (to be incorporated herein by reference). The compounds of the formula I, II, III or IV act here as a UV filter against electrostatic flares. In color photographic materials, the couplers and dyes are also protected against photochemical decomposition.

The present compounds can be used for all kinds of color photographic materials. For example, they can be used for color paper, color reversal paper, direct-positive color material, a color negative film, a color position film, a color reversal film, etc. They are preferably used, inter alia, for photographic color material containing a reversing substrate contains or forms positive.

Color photographic recording materials usually contain, on a support, a blue sensitive and / or a green sensitive and / or a red sensitive silver halide emulsion layer and, if desired, a protective layer, the compounds preferably being either in the green sensitive or the red-sensitive 1007470 21 layer either in a layer between the green-sensitive and the red-sensitive layer or in a layer on top of the silver halide emulsion layers.

The compounds of formula I, II, III or IV can also be used in recording materials based on the principles of photopolymerization, photoplasticisation or micro-capsule rupture, or in cases where heat sensitive and light sensitive diazonium salts, leuko dyes with an oxidizing agent or dye lactones with Lewis acids are used.

Furthermore, they can be used in recording materials for dye diffusion transfer printing, thermal wax transfer printing and non-matrix printing and for use with electrostatic, electrographic, electrophoretic, magnetographic and laser electrophotographic printers and pen plotters. Of the above, recording materials have dye diffusion transfer printing materials. as described, for example, in EP-A-50773 ^. the preference.

They can also be used in ink, preferably for inkjet printing, as further described, for example, in U.S. Patent 5,098,977 (to be considered incorporated herein).

The compounds of this invention exhibit superior hydrolytic stability, handling and storage stability as well as good extractability when present in a stabilized composition.

The process for the preparation of the present compounds is described in the prior art. Most of the intermediates required to prepare the subject compounds are commercially available.

Preferred compounds are those in which one of groups X and Y is -O-; and especially those in which both groups X and Y are —0—. In general, polymers that can be stabilized include 1. Polymers of mono- and diolefins, for example, polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polvisoprene or polybutadiene, as well as polymers of cycloalkenes, such as, for example, 35 of cyclopentene or norbornene; further polyethylene (which may optionally be cross-linked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).

v u 7 4 7 0 22

Polyolefins, ie the polymers of monoolefins shown in the previous paragraph, in particular polyethylene and polypropylene, can be prepared by various, and in particular the following, methods: 5 a) radical polymerization (usually under high pressure and at elevated temperature).

b) by means of a catalyst, the catalyst usually containing one or more metals of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have 10 or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyl groups, alkenyl groups and / or aryl groups, which can have either tt or σ coordination. These metal complexes can be in the free form or they can be fixed on supports, such as, for example, on activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide.

These catalysts can be soluble or insoluble in the polymerization medium. The catalysts may be active as such in the polymerization or further activating agents may be used, such as, for example, metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes, these metal elements being of groups Ia, Ha and / or lilac of the Periodic Table. The activating agents can, for example, be modified with further ester, ether, amine or silyl ether groups. These catalyst systems are commonly known as Phillips, Standard Oil Indian, Ziegler (-

Natta), TNZ (DuPont), metallocene or Single Site Catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different kinds of polyethylene (for example LDPE / HDPE).

3- Copolymers of mono- and diolefins with each other or with other vinyl monomers, such as, for example, ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyvethylene (LDPE), propylene / butylene 1 copolymers. propylene / isobutylene copolymers, ethylene / butene-1 copolymers.

ethylene / hexene copolymers, ethylene / methylpentene copolymers.

ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butane 07 47 0 23 diene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / viacetate copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers), as well as 5 terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norbornene; further mixtures of such copolymers with each other and with polymers mentioned under 1), for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or statistically constructed polyolefin / carbon monoxide copolymers and mixtures thereof with other polymers, such as, for example, polyamides.

4. Hydrocarbon resins (for example, C5-C9), including hydrogenated modifications thereof (e.g., tackifiers) and mixtures of polyolefins and starch.

5 · Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate and 20-methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; high impact blends of styrene copolymers and another polymer such as, for example, a polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and styrene block copolymers such as, for example, styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butene / styrene or styrene / ethylene / propylene / styrene.

7. Graft copolymers of styrene or α-methylstyrene, such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methyl acrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkacrylates resp. alkyl methacrylates on polybutadiene; Styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers, as well as mixtures thereof with the copolymers mentioned under 6), which are known, for example, as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers, such as, for example, polychloropene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin-homo- and copolymers, in particular polymers of halogen-containing vinyl compounds, such as, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers.

9 · Polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, modified with butyl acrylate, impact resistant.

10. Copolymers of the monomers mentioned under 9) with one another or with other unsaturated monomers, such as, for example, acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate copolymers or acrylonitrile / vinyl halide acrylonitrile copolymers / alkylmetha-20 crylate / butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl berzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; 25 as well as their copolymers with the olefins mentioned under 1).

12. Homo- and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

13- Polyacetals such as polyoxymethylene and those polyoxymethylenes containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides and mixtures of polyphenylene-35 oxides with styrene polymers or polyamides.

15 · Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes, on the one hand, and aliphatic or aromatic polyisocyanates, on the other, and their precursors.

• j 0 ü 7 4 7 0 25 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from amino carboxylic acids or the corresponding lactams, such as polyamide-1 *, polyamide-6, polyamide-6/6, - 6/10, -6/9.

-6/12, -4/6, -12/12, polyamide-11, polyamide-12, aromatic polyamides starting from m-xylenediamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid and optionally an elastomer as a modifier, for example poly-2, 4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; as well as condensed polyamides ("RIM polyamide systems") during processing.

17- Polvurea, polyimides, polvamide imides and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylol cyclohexane terephthalate and polyhydroxy benzoates, as well as block copolyether esters derived from polyethers with hydroxyl end groups; further polyesters modified with polycarbonates or MBS.

19 · Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Cross-linked polymers derived from aldehydes on the one hand and phenols, urea or melamines on the other, such as phenol / formaldehyde, urea / formaldehyde and melamine / formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as cross-linking agents, as well as their low-flammability halogen-containing modifications.

24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins cross-linked with melamine resins, urea resins, polyisocyanates or epoxy resins.

26. Cross-linked epoxy resins derived from polyepoxides, for example from bisglycidyl ethers or from cycloaliphatic di-epoxides.

27. Natural polymers, such as cellulose, natural rubber, gelatin and chemically modified homologous derivatives thereof, such as cellulose acetates, propionates and butyrates, respectively. the cellulose ethers, such as methyl cellulose; as well as natural resins and their derivatives.

28. Blends (polyblends) of the aforementioned polymers, such as for example PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, 10 PVC / MBS, PC / ABS, PBTB / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylics, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylic, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO.

29. Natural and synthetic organic materials, which are pure monomeric compounds or mixtures of such compounds, eg petroleum, animal and vegetable fats, oils and waxes, or oils, waxes and fats based on synthetic esters (eg phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with petroleum in any weight ratio commonly used as spinning compositions, as well as aqueous emulsions thereof.

30. Aqueous emulsions of natural or synthetic rubbers, such as e.g. natural rubber latex or latices of carboxylated styrene / butadiene copolymers.

31. Polysiloxanes, such as the soft, hydrophilic polysiloxanes described, for example, in US Patent 4259-667; and the hard polyorganosiloxanes, which are described, for example, in U.S. Pat.

32. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins. The unsaturated acrylic resins include the urethane acrylates, polyether acrylates, vinyl or acrylic copolymers with unsaturated side groups, and the acrylated melamines. The polyketimines are prepared from polyamines and ketones in the presence of an acid catalyst.

33 · Radiation-curable compositions containing ethically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer.

39. Epoxy melamine resins, such as light stable epoxy resins cross-linked with a high solids epoxy-functional, co-etherified melamine resin, such as LSE-4103 (Monsanto).

Generally, the compounds of the present invention are used in an amount of from about 0.01% to about 5% by weight of the stabilized composition, although this varies with the particular substrate and application in question. An advantageous range is from about 0.05 to about 3%, and in particular from 0.05 to about 1%.

The stabilizers of the present invention can be easily incorporated into the organic polymers by conventional techniques for any suitable phase prior to the production of molded articles thereof. For example, the stabilizer in dry powder form can be mixed with the polymer, or a suspension or emulsion of the stabilizer can be mixed with a solution, suspension or emulsion of the polymer. The resulting stabilized polymer compositions of the invention may also optionally contain from about 0.01 to about 5 wt%, preferably from about 0.025 to about 2 wt%, and in particular from about 0.1 to about 1 wt%, of various conventional additives, such as the materials shown below, or mixtures thereof.

20 1. Antioxidants 1.1. Alkylated monophenols. for example.

2.6-di-tert-butyl-4-methylphenol 25 2-tert-butyl-4,6-dimethylphenol 2,6-di-tert-butyl-4-ethylphenol 2,6-di-tert-butyl-4-n-butylphenol 2,6-di -tert-butyl-4-isobutylphenol 2,6-dicyclopentyl-4-methylphenol 30 2- (o-methylcyclohexyl) -4,6-dimethylphenol 2,6-dioctadecyl-4-methylphenol 2,4,6-tricyclohexylphenol 2,6-di-tert-butyl-4 -methoxymethylphenol 1.2, Alkylated hydroquinones. for example.

2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butylhydroquinone 2,5-di-tert-amylhydroquinone 2,6-di phenyl-4-octadecyloxyphenol 1007470 28 1.8. Hydroxylated thiodiphenyl ethers. for example.

2,2'-thiobis (6-tert-butyl-4-methylphenol) 2,2'-thiobis (4-octylphenol) 4,4'-thiobis (6-tert-butyl-3-methylphenol) 5 4,4 ' -thiobis (6-tert-butyl-2-methylphenol) 1.4. Alkylidene bisphenols. for example.

2,2'-methylene bis (6-tert-butyl-4-methylphenol) 2,2'-methylene bis (6-tert-butyl-4-ethyl phenol) 2,2'-methylene bis [4-methyl-6- (a -methylcyclohexyl) phenol] 10 2,2'-methylenebis (4-methyl-6-cyclohexylphenol) 2,2'-methylenebis (6-nonyl-4-methylphenol) 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol] 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4-nonylphenol] 2,2'-methylenebis (4,6-di-tert-butylphenol) 2,2'-ethylidene bis (4,6-di-tert-butylphenol) 2,2'-ethylidene bis (o-tert-butyl-4-isobutylphenol) 4,4'-methylene bis (2,6-di-tert-butylphenol) 4,4'- methylene bis (6-tert-butyl-2-methyl phenol) 1,1-bis (5 "tert-butyl-4-hydroxy-2-methylphenyl) butane 20 2,6-bis (3-tert-butyl-5-methyl-2 -hydroxybenzyl) -4-methylphenol 1,1,3-tris (5 * tert-butyl-4-hydroxy-2-methylphenyl (butane 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3 n-dodecyl mercapto-butane ethylene glycol bis [3,3 "bis (3'-tert-butyl-4'-hydroxyphenyl (butyrate) 25 di (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene di [ 2 - (3 '- tert-buty 1-2' -hydroxy-5 '-me thylbenzyl) -6-tert-butyl-4-methyl-phenyl] terephthalate 1.5. Benzyl compounds, for example.

1,3 · 5 "tri (3.5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene 30 di (3.5" di-tert-butyl-4-hydroxybenzyl (sulfide 3.5-di-tert -butyl-4-hydroxybenzyl mercaptoacetic acid isooctyl ester bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzy1 (dithiol terephthalate 1,3.5 "tris (3.5-di-tert-butyl-4-hydroxybenzyl) isocyanurate 1,3 · 5" tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate 35 3,5-di-tert-butyl-4-hydroxybenzylphosphoric acid dioctadecyl ester 3.5-di-tert-butyl-4-hydroxybenzylphosphoric acid monoethyl ester, calcium - salt 1, 6. Acvlaminophenols, for example.

I 7 4 7 0 29 4-hydroxylauric anilide 4-hydroxystearic anilide 2,4-bis-octyl mercapto-6- (3.5-tert-butyl-4-hydroxyanilino) -s-triazine octyl-N- (3.5-di-tert-butyl-4- hydroxyphenyl) carbamate 5 1.7. Esters of B-n.S-di-tert-butyl-phenylhydroxyphenyl-Dropionic acid with mono- or polyhydric alcohols, for example, methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediol pentaerythritol 10-neopentyl glycol trihydroxyethyl isocyanurate thiodiethylthylamino-dihydroethyl-1,8 Esters of B- (c-tert-butyl-tl-hydroxyd-3-methylphenyl] -pole ionic acid with monohydric or polyhydric alcohols, for example, methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopentyl glycol triethyl diethyl amine thiodiethethyl amine. - (^ R-di-tert-butyl - ^ - hydroxylphenyl) propionic acid, for example, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine N, N'-bis ( 3 -5 "di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine N, N'-bis (3,5" di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine 1.10. Diarvlamines, for example, diphenylamine, N-phenyl-1 -naphthylamine, N- (4-tert-octylphenyl) -1-naphthyllamine, 4,4'-di-tert-octyldiphenylamine, reaction product of N-phenyl-30-benzylamine and 2,4,4-trimethylpentene, reaction product of diphenylamine and 2,4,4-trimethylpentene, reaction product of N-phenyl-1-naphthylamine and 2.4.4-trimethylpentene 2. UV absorber and and light protection agents 2.1, 2- (2'-hydroxyphenvDbenztriazoles. for example, the 5'-methyl-, 3'5'-di-tert-butyl-. 5'-tert-butyl-, 5 '- (1,1,3,3-tetramethylbutyl) -, 5-chloro-3', 5'-di-tert-butyl, 5-chloro-3'-tert- butyl-5'-methyl-, 3'-1007470 30 sec-butyl-5'-tert-butyl, V-octoxy, 3'.5'-di-tert-amyl-, 3'.5 '"bis - (α, α-dimethylbenzyl) -, 3'-tert-butyl-5 '- (2- (omega-hydroxy-oc ta- (ethyleneoxy) carbonylethyl) -, 3'-dodecyl-5'-methyl- and 3 1-tert-butyl-5 '- (2-octyloxycarbonyl) ethyl and dodecylated 5'-methyl derivatives.

5 2.2. 2-hydroxybenzophenones. for example the 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, -benzyloxy-, 4,2 ', 4-trihydroxy- and 2'-hydroxy- ^, ^ dimethoxy derivative.

2.3. Esters of optionally substituted benzoic acids. for example, phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate, 10-dibenzoyl resorcinol, bis (t-tert-butylbenzoyl) resorcinol, benzoyl resor cinol, 3i-5-tert-butyl-4-hydroxy-benzoic acid t-2-di-phenylvi ter and 3.5 "di-tert-butyl-hydroxy-benzoic acid hexadecyl ester.

2.k. Acrvaten. for example, α-cyano-β, β-diphenylacrylic acid ethyl ester, respectively. isooctyl ester, α-carbomethoxy cinnamic acid methyl ester, α-cyano-β-15 methyl p-methoxy cinnamic acid methyl ester, respectively. -butyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N - (carb-carbomethoxy-p-cyano-vinyl) -2-methylindoline.

2.5. Nickel compounds. for example nickel complexes of 2,2'-thio-bis [4- (1,1,3,3 "tetramethylbutyl) phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ligands, such as n butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyl dithioca bamate, nickel salts of the monoalkyl esters, eg the methyl, ethyl or butyl ester, of A-hydroxy-3,5 "di-tert-butylbenzylphosphonic acid, nixkel complexes of ketoximes, such as of 2-hydroxy-methylphenyl undecyl-ketoxime, nickel complexes of 1-phenyl-14-lauroyl -5-hydroxypyrazole, optionally with additional ligands.

2.6. Sterically hindered amines. for example, bis (2,2,6,6-tetra-methylpiperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid -bis (1,2,2,6,6-pentamethylpiperidyl) ester, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-^ -hydroxypiperidine and succinic acid, the condensation product of N, N'-bis (2,2,6,6-tetramethylpiperidyl) hexamethylene diamine and A-tert-octylamino-2,6-dichloro-s-triazine, tris (2,2,6,6-tetramethylpiperidyl) ni trilo tri acetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3, - butane tetracarboxylate, 1,1 '- (1,2-ethanediyl) bis (3.3.5.5 "tetramethylpiperazinone) bis (1-octyloxy-2,2,6,6-tetra-methylpiperidin-1-yl) sebacate.

2.7. Oxalic acid diamides. for example 4, k'-dioctyloxyoxanilide, 2,2'-1v / 4 7 0 31 dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2 -ethoxy-2'-ethyl oxanilide, N, N'-bis (3-dimethyl-aminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyl oxanilide and the mixture thereof with 2-ethoxy-2'-ethyl -5, -1- di-tert-butyloxanilide and 5 mixtures of o- and p-methoxy- as well as o- and p-ethoxy-di-substituted oxanilides.

2.8. Hydroxyphenyl s triazines. for example 2,6-bis (2,1-dimethyl-phenyl) -h- (2-hydroxy-octyloxyphenyl) -s-triazine; 2,6-bis (2,4-dimethylphenyl) -4- (2,4-dihydroxyphenyl) s-triazine; 2,4-bis (2,4-dihydroxyphenyl) -10 6 - (1-chlorophenyl) -s-triazine; 2, it-bis [2-hydroxy-14- (2-hydroxyethoxy) -phenyl] -6-chlorophenyl) -s-triazine; 2, ii-bis [2-hydroxy-4- {2-hydroxyethoxy) phenyl] -6- {2,4-dimethylphenyl) -s-triazine; 2,4-bis [2-hydroxy- (2-hydroxyethoxy) phenyl] -6- (bromophenyl) -s-triazine; 2, ^ - bis [2-hydroxy - ^ - (2-acetoxyethoxy) phenyl] -6 - (^ - chlorophenyl) -s-triazine, 2,1 k-bis (2,4-dihydroxyphenyl) -6- (2,4-dimethylphenyl) s-triazine.

3. Metal deactivators. for example, N. N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3.5-di-tert-butyl-k-hydroxyphenylpropionyl) hydrazine, 3 ~ salicycloylamino-1,2, triazole, bis (benzylidene) oxalic acid dihydrazide.

20 * 4. Phosphites and Phosphonites. for example, triphenylphosphite, diphenylalkylphosphites, phenyl dialkylphosphites, tris (nonylphenyl) phosphite, tri-laurylphosphite, trioctadecylphosphite, distearylpentaerythritol diphosphite, 2-di-tert-butylphenylphthisodiphosphodylphosphorus) * 4,6-tri-tert-butylphenyl) pen taerythritol diphosphite, di (2,14-di-t-butyl-6-methyl phenyl) pentaerythritol diphosphite di (2,1,6-di-tert-butylphenyl pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -k, 4'-diphenylylene diphosphonite.

5. Peroxide-destroying compounds, for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole, the zinc salt of 2-mercapto-benzimidazole, zinc-dibutyl dithiocarbamate, dioctadecythythritol-tentaethylthisulfenta-pentaethyldisulfide (6-dodecyl mercapto) propionate.

6. Hvdroxvlamines. for example, Ν, Ν-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxyl-amine, Ν, Ν-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dylthylamine hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octacecylhydroxylamine, Ν, Ν-dialkylhydroxylamine from hydrogenated tallow fatty amine.

1007470 32 7. Nitrons. for example N-benzyl-alpha-phenyl-nitron, N-ethyl-alpha-methyl-nitron, N-octyl-alpha-heptyl-nitron, N-lauryl-alfa-undecyl nitron, N-tetradecyl-alpha-tridecyl nitron, N-hexadecyl-alpha-pentadecyl nitron, N-octadecyl-alpha-heptadecyl-nitron, N-hexadecyl-alpha-heptadecyl-nitron, 5 N-octadecyl-alpha-pentadecyl-nitron, N-heptadecyl-alpha-heptadecyl-nitron, N-octadecyl-alpha-hexadecyl-nitron, nitronyl nitron, nitronyl hydrogenated sebum fatty amine.

8. Stabilizers for polyamide, for example copper salts in combination with iodides and / or phosphorus compounds and salts of bivalent manganese.

9. Basic co-stabilizers. for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg stearate, Na stearate ricinoleate and K palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

10. Nucleating agents, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.

11. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

12. Other additives, for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents and thiosynergists such as distalyl thiodipropionate or distearyl thiodipropionate.

13. Benzofuranones resn. indolinones. for example, those described in US-A-32585863. US-A-433O299 or US-A-5175312, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl- 3 - [^ - (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7 ~ 30 di-tert-butyl-3 - (^ - [2-hydroxyethoxy] phenyl) benzofuran-2- on], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3 ((--acetoxy-3,5-dimethylphenyl) ~ 5,7-di-tert- butylbenzofuran-2-one, 3 "(3.5" dimethyl-piva-loyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2-one.

The co-stabilizers, with the exception of the benzofuranones mentioned under 13, are added, for example, in concentrations of 0.01 to 10% with respect to the total weight of the material to be stabilized.

Further preferred compositions comprise, in addition to 1007470 33 components (a) and (b), further additives, in particular phenolic antioxidants, light stabilizers or processing stabilizers.

Particularly preferred additives are phenolic antioxidants (part 1 of the list), sterically hindered amines 5 (part 2.6 of the list), phosphites and phosphonites (part ^ of the list) and peroxide destroying compounds (part 5 · of the list) .

Also particularly preferred additional additives (stabilizers) are benzofuran-2-ones, which are described, for example, in US-A-325863, US-A-3382, or US-A-5175312.

The phenolic antioxidant of particular interest is selected from the group of n-octadecyl-3,5 "di-tert-butyl-hydroxyhydrocinnamate, neopentaantetrayl-tetrakis (3,5-di-tert-butyl-hydroxyhydrocinnamate) , di-n-octadecyl-3,5 "di-tert-butyl-hydroxy-benzyl-15-phosphonate, 1,3,5'-tris (3,5" di-tert-butyl-hydroxy-benzyl) -isocyanurate, thiodiethylene- bis (3,5'-di-tert-butyl-A-hydroxyhydrocinnamate), 1,3,5-trimethyl-2, k, 6-tris {3.5-di-tert-butyl-hydroxybenzyl) benzene, 3,6-dioxaoctamethylene-bis (3 -methyl-5'-tert-butyl-A-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene bis (4,6-di-tert-butylphenol) 1,3.5'tris (2,6-dimethyl-A-tert-butyl-3 "hydroxybenzyl) isocyanurate, 1,1,3'tris (2-methyl-il-hydroxy-5-tetr-butylphenyl) butane, 1 3.5 'tris [2- (3.5 "di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl isocyanurate, 3.5" di (3.5'di-tert-butyl-4-hydroxybenzyl) mesiol, hexamethylenebis (3 5-di-tert-butyl-14-hydroxyhydrocinnarate), 1- (3,5'-di-tert-butyl-4-hydroxyanilin o) -3.5 "di (octylthio) -s-triazine, N, N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis (ethyl-3,5-di- tert-butyl-hydroxybenzylphosphonate), ethylene bis [3.3 "di (3" tert-butyl-hydroxyphenyl) butyrate], octyl-3,5'-di-tert-butyl-hydroxybenzyl mercaptoacetate. bis (3,5'-di-tert-butyl-1-hydroxyhydro-30-cinnamoyl) hydrazide and N, N'-bis [2- (3.5'-di-tert-butyl-2-hydroxyhydro-cinnamoyloxy) ethyl oxamide.

A particularly preferred phenolic antioxidant is neopentaantetrayl-tetrakis (3,5'-di-tert-butyl-hydroxyhydrocinnamate), n-octadecyl-3'-di-tert-butyl-hydroxy-hydrocinnamate, 1,3.5-trimethyl- 35,2,6,6-tris (3,5 "di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3.5-di-tert-butyl-hydroxybenzyl) isocyanurate, 2,6-di -tert-butyl-p-cresol 1 or 2,2'-ethylidene-bis {k, 6-di-tert-butylphenol).

The sterically hindered amine compound of special interest 100/470 34 is selected from the group of bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6 pentamethylpiperidin-4-yl) sebacate, di {1,2,2,6,6-pentamethylpiperidin-4-yl) - (3,5 "di" tert-butyl-4-hydroxy-5-benzyl) butylmalonate, 4- benzoyl-2,2,6,6-tetraraethylpiperidine, 4-stearoyl-2,2,6,6-tetramethylpiperidine, 3 "t-octyl-7,7,9,9-tetramethyl-1,3,8 -triaza- spiro [4.5] decane-2,4-dione, tris (2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, 1,2-bis (2,2,6,6-tetramethyl-3- oxopiperazin-4-yl) ethane, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro [5.1.11.2] heneicosan, the polycondensation product of 2,4-dichloro-6-tert -octylamino-s-triazine and 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine), the polycondensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4 - Hydroxypiperidine and succinic acid, the polycondensation product of 4,4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine) e n 1,2-dibromoethane.

tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) -1,2,3,4-butane tetracarboxylate, 20 tetrakis (1,2,6,6,6-pentamethylpiperidin-4-yl) -1 2,3,4-butane tetracarboxylate, the polycondensation product of 2,4-dichloro-6-zorpholino-s-triazine and 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine), N, N ', N ", N" "-tetrakis [(4,6-bis (butyl-1,2,2,6,6-pentamethylpiperidin-4-25 yl) amino-s-triazin-2-yl] -1 10-diamino-4,7-diazadecane, mixed [2,2,6,6-tetramethylpiperidin-4-yl / | 3, β, 6'β'-tetramethyl-3,9- (2,4,8, 10-tetraoxaspiro [5.5] undecane) diethyl] -1,2,3,4-butane-tetra-carboxylate, mixed [1,2,2,6,6-pentamethylpiperidin-4-yl / 6, β, β'β'- tetramethyl-30 3.9- (2,4,8,10-tetraoxaspiro [5 · 5] undecane) diethyl] -1,2,3,4-butane tetracarboxylate, octamethylene bis (2,2,6,6-tetramethylpiperidine-4-car -boxylate), 4,4'-ethylene bis (2,2,6,6-tetramethylpiperazin-3-one), N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide, Nl, 2,2,6,6-pentamethyl-35-piperidin-4-yl-n-dodecylsuccinimide, Nl-acetyl-2 2,6,6-tetramethyl-piperidin-4-yl-n-dodecylsuccinimide, 1-acetyl-3-dodecy1-7,7.9.9 "tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4 -dione, di (1-oc tyloxy- 2,2,6,6-tetramethylpiperidin-4-yl) sebacate, di (1-cyclohexyloxy-1007470 35 2,2,6,6-tetramethylpiperidin-1-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-^ -hydroxypiperidine, poly {[6-tert-octylamino-s-triazine-2,2-diyl] [2- (1-cyclohexyloxy-2,2,6) 6-tetramethylpiperidine-1-yl) imino-hexamethylene [4- (1-cyclohexyloxy-2,2,6,6-tetramethyl-1-piperidin-k-yl) -5 imino] and 2,4,6-tris [N - (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -n-butylamino] -s-triazine.

A particularly preferred sterically hindered amine compound is bis (2,2,6,4-tetramethylpiperidin-A-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di ( 1,2,2,6,6-penta-10 methylpiperidin-A-yl) - (3 <5-di-tert-butyl-4-hydroxybenzyl) butyl malonate, the polycondensation product of 1- (2-hydroxyethyl) - 2,2,6,6-tetramethyl - ^ - hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and ^, V-hexa-methylenebis (amino-2,2,6 , 6-tetramethylpiperidine), N, K ', N ", N'" -tetra-15 kis [(A, 6-his (butyl (1,2,2,6,6-pen tame t hy 1 piper i dine) - 4-yl) amino) -s-tri-azin-2-yl] -1,110-diamino-4,7-diazadecane, di (1-octyloxy-2,2,6,6-tetra-methylpiperidine-4 -yl) sebacate, di (1-cyclohexyloxy-2,2,6,6-tetramethyl-1-piperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, poly { [6-tert-octylamino-s-triazin-2,2-diyl] [2- (1-20-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) iminohexamethylene [4- (1-cyclohexyloxy-2) , 2,6,6-t etramethylpiperidin-A-yl) imino] or 2,6-tris [K- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-1-yl) -n-butyl-amino] -s-triazine.

The present composition may additionally contain other UV absorbers selected from the group of the s-triazines, the oxanilides, the hydroxybenzophenones, the benzoates and the α-cyanoacrylates.

In particular, the present invention can additionally contain an effective stabilizing amount of at least another 2-30 hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; or contain a sterically hindered amine or mixtures thereof.

Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected from the group of 2- (2-hydroxy-3.5 "di-tert-amylphenyl) -2H-benzotriazole; 2- [2-hydroxy-3,5 "di (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole; 2- [2-Hydroxy-3_ (Q, Q-dimethylbenzyl) -5-octylphenyl] -2H-benzotriazole; 2- {2-hydroxy-3-tert-butyl-5- [2- (omega-hydroxy-octa (ethyleneoxy) -carbonyl) ethyl] phenyl} -2H-benzotriazole; and 1007470 36 2- {2-hydroxy-3 "tert-butyl-5" [2- (octyloxy) carbonyl) ethyl] phenyl} -2H-benzotrlazole.

Preferably the other tris-aryl-s-triazine is selected from the group of 5 2-bis (2-dimethylphenyl) -6- (2-hydroxy-**-octyloxyphenyl) -s-triazine; 2,1-diphenyl-6- (2-hydroxy-A-hexyloxyphenyl) s-triazine; 2,9-bis {2,4-dimethylphenyl) -6 - [2-hydroxy - (3-do- / tridecyloxy-2-hydroxypropoxy) -phenyl] -s-triazine; and 2- (2-hydroxy ethyl amino) -4,6-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-10-tetramethylpiperidin-4-yl) amino] s-triazine.

The alkyd resin paints which can be stabilized according to the present invention against the action of light and moisture are the usual stoving paints, which are used in particular for painting cars (car finishing paints), for example paints based on alkyd / melamine resins and alkyd / acrylic / melamine resins (see H. Wagner and HF Sarx, "Lackkunstharze" (1977). pages 99-123) -Other cross-linking agents include glycouril resins, blocked isocyanates or epoxy resins.

The paints stabilized according to the invention are suitable for both metal finishing paints and solid color top coat, in particular in the case of retouching top coat, as well as various coil coat applications. The lacquers stabilized according to the invention are preferably applied in the usual manner by two methods, either the single coating method or the double coating method. In the latter method, the pigment-containing base coat is first applied and then a covering lacquer or clear coat.

It should further be noted that the compounds of the present invention are useful for use in non-acid catalyzed thermosetting resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyester resins optionally modified with silicon , isocyanates or isocyanurates. The epoxy and epoxy polyester resins are cross-linked with conventional cross-linking agents such as acids, acid anhydrides, amines and the like. Accordingly, the epoxide can be used as the cross-linking agent for various acrylic or polyester resin systems modified with reactive groups on the backbone structure.

When used in two-coat coatings, the compounds 1007470 37 of the present invention can be incorporated into the clear coat or both into the clear coat and the pigmented base coat.

When water-soluble, water-miscible or water-dispersible lacquers are desired, ammonium salts of the acid groups present in the resin are formed. Powder coating compositions can be prepared by reacting glycidyl methacrylate with selected alcohol components.

The present benzotriazoles are prepared by conventional methods for the preparation of such compounds. The usual method involves the diazotization of a substituted o-nitroaniline, followed by coupling the obtained diazonium salt with a substituted phenol and reduction of the azo-benzene intermediate to the corresponding desired benzotriazole. The starting materials for these benzotriazoles are in large part commercially available compounds or can be prepared by normal organic synthesis methods.

Since the present benzotriazoles with their improved durability are particularly suitable for use in automotive paints, they are contemplated to be particularly useful in other applications where their improved durability is required, such as in sun films and the like.

The following examples are for illustrative purposes only.

Example I

25

Preparation of 5-Trifluoromethyl-2- (2-hydrochloride-3-alpha-5-tert-octyl-phenyl) -2H-benzotriazole a) Diazotization of -amino-3-nitrobenzotrifluoride 30

To a 500 ml 3 "neck flask equipped with a mechanical stirrer are added 1.2 g of amino-3-nitrobenzotrifluoride, 52 ml of concentrated hydrochloric acid and 100 ml of distilled water. The stirred solution is cooled to 5 ° 0 and 17.3 g of sodium nitrite dissolved in 50 ml of water are added. The solution is stirred at 0 to 5 ° C for two hours, then filtered and stored at -10 ° C.

100/470 38 b) Monoazo reagent

To a 1000 ml flask equipped with a mechanical stirrer, 40 g of sodium hydroxide dissolved in 200 ml of methanol and 5 32.4 g of 2-α-cumyl-4-tert-octylphenol in 50 ml of xylene are added. The solution is cooled to 5 ° C and the diazo solution of 4-amino-nitro-benzotrifluoride prepared in part a. Is added over a period of two hours at 0 to 5 ° C. Then, 100 ml of xylene is added and the organic layer is washed with water, aqueous hydrochloric acid, water, an aqueous sodium hydrogen carbonate solution and finally water. The solvent is removed under reduced pressure and the residue is purified by chromatography (silica gel, heptane-ethyl acetate 95-5). whereby 42.1 g of the reaction product are obtained as a dark red paste.

C) Reduction of the monoazo reagent

A 1000 ml flask is charged with 20 g of sodium hydroxide, 40 ml of water, 42.1 g of the portion b. prepared monoazo reagent and 400 ml of ethanol. The mixture is heated to 80 ° C and 27 g of formamidine sulfinic acid are added in portions with stirring. After 1.5 hours, the solution is cooled to room temperature and 100 ml of water are added. The pH is adjusted to 7 with concentrated hydrochloric acid. The ethanol is removed in vacuo and the water layer is extracted with dichloromethane. The solvent is then evaporated under vacuum and the residue is purified by chromatography (silica gel, heptane: toluene 9 · ·) and crystallized from methanol. The title compound is obtained in a yield of 5-6 g as a pale yellow solid melting at 119-121 ° C.

30

Example II

Preparation of tS-fluoro-2- (2-hvdroxv-3-a-cumvi-5-tert-octylphenyl) -2H-benzotriazole 35

The title compound is prepared using 31.2 g of 4-fluoro-2-nitroaniline by the general procedure of Example I. In part c of the process, an additional 9 g of formamidine sulfinic acid is required to complete the reduction. Purification of the crude product over silica gel (heptane: toluene, 1: 1) affords 9.5 g of the title compound as an off-white solid. Further purification by recrystallization from acetonitrile: toluene gives 1.1 g of the title compound which melts at 93 ° 96 ° C.

Example III

Preparation of 5-chloro-2- (2-hvdroxv-Va-cumvl-Ej-tert-octvlfenvl) -2H-10 benzotriazole

Parts a and b of the general procedure of Example I are followed to prepare the monoazo intermediate to prepare the title compound from 339.3 g of 9-chloro-2-nitroaniline. The crude product is purified by recrystallization from methanol to give 70.9 g of the dark red monoazo reagent.

c) Reduction of the monoazo reagent 20 A mixture of 11.8 g of sodium hydroxide and 138 g of 2-butanol is heated to 95'0 · A solution of 60.1 g of the above monoazo reagent and 1.3 g of 2, 3-Dichloro-1,9-naphthoquinone in 90 g of 2-butanol is added with stirring over 90 minutes. The reaction mixture is heated to remove the 2-butanone by-product, adding additional 2-25 butanol to replace the distillate. The reaction mixture is cooled to 85 ° C, washed with 2.5N sulfuric acid and brine and then concentrated. The residue is recrystallized from methanol: xylene to obtain 95.6 g of the title compound as a pale yellow solid melting at 109-105 ° C.

30

Example IV

Preparation of 5-phenylthio-2- (2-hvdroxv-3-o-cumvl-5-tert-octvlphenvl) -2H-benzotriazole 35

A mixture of 5-chloro-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole and 105 g of N-methylpyrrolidone is first stirred and heated to 90 ° C over a period of 15 minutes 99.3 g of 1007470 40 a 45 # aqueous potassium hydroxide solution and then 20.4 g of thiophenol over 15 minutes. The reaction mixture is then heated to 170-175 ° C for four hours, water being removed by distillation. After cooling to 100 ° C, xylene and water are added and the resulting mixture is acidified with a 15% aqueous hydrochloric acid solution. The organic layer is separated and washed with water and then concentrated. The crude product residue is recrystallized from methanol to give 82 g of the title compound as a pale yellow solid, melting at 124-125 ° C.

10

Example V

Preparation of 5-benzenesulfon-2-f2-hvroxv-Vo-cumyl-i:) - tert-octyl-phenyl) -2H-benzotriazole 15

A 1000 ml flask is charged with 75.2 g of 5-phenylthio-2- (2-hydroxy-3 "Q" Cumyl-5-ter-octylphenyl) -2H-benzotriazole, prepared in Example IV, 102 g of xylene, 0.9 g of sodium tungstate dihydrate and 18.4 g of formic acid. The mixture is heated to 50 ° C. 36.3 g of 50% hydrogen peroxide are slowly added to this stirred mixture so that the temperature does not exceed 85 ° C. Additional xylene and water are then added. The organic layer is separated, washed with aqueous sodium sulfite, then twice with water and concentrated. The crude product residue is recrystallized from methanol to give 75.2 g of the title compound as a pale yellow solid, melting at 170-171 ° C.

Example VI

Preparation of 5-nonvIthio-2- (2-hvdroxv-3-Q-cumvl-5-tert-octvlfenvl1-2H-benzotriazoo]

The title compound is prepared with 30 g of 5-chloro-2- {2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole and 17.6 g of nonyl mercaptan 35 using the procedure of Example IV.

Example VII

1007470 4i

Preparation of 5-non.vlsulfonvl-2- (2-hvdroxv-Vq-cumvl-B-tert-octvl-

fenvl) -2H-benzotriazole

5-Nonylthio-2- {2-hydroxy-3-α-cumyl-5'-tert-octylphenyl) -2H-benzo-5-triazole, prepared in Example VI, without purification of the thio intermediate using 8.7 g of formic acid, 0.7 g of sodium tungstate dihydrate and 17.6 g of 50% hydrogen peroxide oxidized to the sulfone to yield the title compound as a pale yellow resin with a molecular ion ratio of m / e 631.

10

Example VIII

Preparation of 5-chloro-2- (2-hvdroxv-5-phenyl-5-tert-octylphenyl) -2H-benzotriazole 15

Parts a and b of the general procedure of Example 1 are used to prepare the monoazo intermediate for the title compound from 4-chloro-2-nitroaniline and 2-phenyl-4-tert-octyl-phenol. The crude product is purified by recrystallization from methanol to give a dark red monoazo reagent.

The title compound is prepared according to the reduction method of Example III from 65 g of the monoazo reagent prepared above, 19.9 g of sodium hydroxide and 2.4 g of 2,3-dichloro-1,4-naphthoclone. The crude product is purified by silica gel chromatography (hexane: ethyl acetate, 5 = 1) to give a fraction consisting essentially of the title compound with a molecular ion ratio of m / e 433 ·

Example IX 30

Preparation of 5-phenylthio-2- (2-hvdroxv-Vfenvl-5-tert-octvlfenvI) -2H-benzotriazole

The title compound is prepared according to the procedure of Example IV from 20 g of the compound of Example VIII, 20.4 g of 45% aqueous potassium hydroxide, 10.3 g of thiophenol and 100 g of N-methylpyrrolidone. The title compound is an oil which is purified by silica gel chromatography using toluene as the eluent.

1007470 5 42

Example X.

Preparation of H-Benzenesulfonyl · ^ - (2-Hdroxv-Vfenvl-5-tert-octvl-Fenvl) -2H-Benzotriazole

The title compound is prepared according to the procedure of Example V from 20 g of the thio compound of Example IX, 6.4 g of formic acid, 15.0 g of 50¾ hydrogen peroxide and 0.6 g of sodium tungstate dihydrate. Recrystallization from 2.5 g of the crude material xylene / methanol 10 gives 2.0 g of the purified title compound as a pale yellow powder melting at 204-206 ° C.

Example XI

Preparation of a mixture of h-chloro-2- (2-hydroxyl-3,5-dialkylphenyl) -2H-benzotriazole (wherein the alkyl is independently C / ,, Ca, C12 and Clf)

A mixture of 65.4 g of 5-chloro-2- (2-hydroxy-3,5-dialkylphenyl) -2H-benzotriazole, 45 ml of dodecene and 13 ml of methanesulfonic acid is heated to 170 ° C under nitrogen. A further 135 ml of dodecene is added over a 4.5 hour period. The reaction mixture is allowed to cool to 100 ° C and then it is quenched with 400 g of crushed ice and extracted three times with ethyl acetate. The organic layers are combined and washed with water, aqueous sodium hydrogen carbonate, water again and brine, dried over anhydrous magnesium sulfate and finally concentrated. The polymer residue is removed under vacuum at 0.2 mm and up to 210 ° C by distillation from flask to flask. Unreacted starting material is then removed by distillation (at 0.01 mm, 160 ° C) to give 45 g of the title mixture as a yellow oil.

Example XII

Preparation of a mixture of c 1 -phenylthio-2- (2-hydroxyl-b-dialkyl-35-phenyl) -2H-benzotriazole (wherein the alkyl is independently C 1, C 5, Cir and

Cib-iS)

The title mixture is prepared using 40 g of the mixture of 1 X 07 A7 0 43 Example XI, 11.2 g of potassium hydroxide and 12.3 ml of thiophenol according to the procedure of Example IV.

Example XTTT

5

Preparation of a mixture of 5-benzenesulfon-2-2- (2-hydroxyl-5-dialkylphenyl) -2H-benzotriazole (wherein the alkyl is independently C 1 -C 8 yl.

£ 12 g Cl6_is) A mixture of the crude product of Example XII, 350 ml of isopropanol, 14.7 ml of formic acid and 1.8 ml of concentrated sulfuric acid is refluxed and 30 ° 1 is added dropwise over a period of two hours. 50% hydrogen peroxide added. After refluxing for an additional three hours, the reaction mixture is cooled and 10% aqueous sodium sulfite and aqueous sodium hydrogen carbonate are added. Isopropanol is evaporated and the residue is extracted with dichloromethane. The organic layer is washed with water and then dried over anhydrous magnesium sulfate. The solution is concentrated to leave 45 g of crude product as a viscous oil. 30 g of this crude product are purified by silica gel chromatography (heptane: ethyl acetate, 4: 1) to give 28.9 U of the title mixture as a yellow oil.

Example XIV

5-diphenylphosphinyl-2- (2-hvdroxv-3.5-tert-butylphenyl) -2H-benzotriazole

In a flame-dried three-necked round-bottomed flask of 500 ml, equipped with a condenser, a magnetic stirrer and a thermometer, 100 ml of dimethyl sulfoxide, 7.4 l g (0.066 mol) of potassium tert are added via syringe. butoxide and 11.17 g (0.060 mol) of diphenylphosphine. A suspension of 10.56 g (0.030 mol) of 5-chloro-2- (2-hydroxy-3,5 "di-35 tert-butylphenyl) -2H-benzotriazole in 50 ml of dimethyl sulfoxide is added to the red mixture in one go. . The resulting brown solution is stirred at 135 ° 0 for 3.5 hours and then cooled to room temperature. The mixture is quenched with a portion of a saturated ammonium chloride solution

kH

and then ethyl acetate is added. The organic layer is separated and washed three times with water and once with brine, then dried over anhydrous magnesium sulfate. 50% hydrogen peroxide is added to the solution, resulting in an exothermic reaction. The mixture is kept for 30 minutes, after which it is washed once with a 10¾'s sodium metabisulfite solution, three times with a saturated sodium hydrogen carbonate solution and once with a salt solution and finally dried over anhydrous magnesium sulfate. The mixture is filtered with a plug of silica gel and the solvent is removed under reduced pressure to yield 8.0 g of a crude yellow solid. The crude product is treated by medium pressure chromatography using heptane: ethyl acetate, 1: 1, k, 2 g (27% yield) of the title compound as a yellow solid, melting at 98-100 ° C C, is obtained.

Example XV

5-diphenvlphosphin invl-2 - (2-hvdroxv-3-o-cumvl -5 - tert-oc tvl fenvl) -2H-benzo-20 triazole

The title compound is prepared from 5-chloro-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzo-triazole as starting benzotriazole intermediate according to the procedure of Example XIV.

25

Examples XVI-XXVI

The following additional 2H-benzotriazoles carbon black Formula I 'are prepared according to the general procedure of Example I.

1 ΰ 0 7 4 7.0 45

Example G2 Ej E2 XVI CF3 phenyl tert-octyl 5 ----- XVII CF3 a-cumyl tert-butyl XVIII CN a-cumyl tert-octyl 10 XIX CN a-cumyl nonyl XX CN a-cumyl tert-butyl XXI COOCH, a-cumyl dodecyl 15 ---- XXII F phenyl tert-octyl XXIII CF3 a-cumyl nonyl 20 XXIV CF3 a-cumyl dodecyl XXV C0N (Bu) 2 a-cumyl tert-octyl XXVI COOphenyl tert-octvl 25 - -: -

Example XXVIT

Preparation of 5-octylthio-2- (2-hvroxv-Va-cumvl-5-tert-octvlfenvl) -30 2H-benzotriazole

The title compound is prepared using the procedure of Example VI with 5-chloro-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole and octyl mercaptan.

35

Example XXVITT

Preparation of 5-octylsulfon-2-2- (2-hydroxyl-3-a-cumyl-5-tert-octyl-phenyl) -2H-benzotriazole 40 5-octylthio-2- {2-hydroxy-3-α-cumyl-5 -tert-octylphenyl) -2H-benzo-triazole, prepared in Example XXVII, is oxidized to the sulfone without purification of the thio intermediate by the general procedure of Example VII.

45

Example XXIX

1 ü 0 7 A 7 0 46

Preparation of 6-chloro-2- (2,4-dihydroxyphenyl) -2H-benzotriazole

The monoazo intermediate of the title compound is prepared from 17.3 g of 4-chloro-5-2-nitroaniline according to the general procedure of Example 1, parts a L b, whereby 3, 7 g of a wet cake of a dark red monoazo reagent is obtained.

Reduction of the monoazo reagent. A mixture of 20 g of sodium hydroxide, 500 ml of water and 26.3 g of the wet cake of the monoazo reagent prepared above is heated to 30 ° C. Zinc powder (33.0 g) is added incrementally over two hours. At the end of this addition, 180 g of a 50% aqueous sodium hydroxide solution are added dropwise over an hour. The mixture is stirred at ambient temperature for 96 hours. The zinc residue is removed by filtration. The aqueous solution is neutralized to pH 5-6 and the resulting suspension is filtered. The resulting filter cake is washed well with water and dried, yielding 22.5 g of crude product. The crude product is purified by Soxhlet extraction with acetone to obtain 9.6 g of the title compound.

Example XXX

25 Preparation of E-chloro-2- (2-hvdroxv-4-octflxvfenvl) -2H-benzotriazole

A mixture of 6.5 g of 5-chloro-2- (2,4-dihydroxyphenyl) -2H-benzo triazole, 7.1 g of 1-bromoctane, 5.2 g of anhydrous potassium carbonate and 100 ml of acetone is refluxed for 24 hours. About 100 ml of water and ethyl acetate are added to the resulting mixture and 10.6 g of crude product is isolated, column chromatography using petroleum ether gives 0.9 g of the title compound, the structure of which is confirmed by H -NMR and mass spectroscopy.

35

Example XXXI

Preparation of E-trifluoromethyl-2- (2,4-dihydroxyphenyl) -2H-henzotriazole i u / A / 0 47

The title compound is prepared according to the general procedure of Example XXIX from 10.3 g of 4-amino-3-nitrobenzotrifluoride to yield 6.4 g of the title compound, whose structure is confirmed by H-NMR.

5

Example XXXTT

Preparation of S-trifluoromethyl-2- (2-h-hydroxv-4-octl-xfl-phenyl) -2H-benzo-triazole 10

The title compound is prepared from 5.6 g of 5-trifluoromethyl-2- (2,4-dihydroxyphenyl) -2H-benzo-triazole according to the general procedure of Example XXX. The crude product is purified by column chromatography to give 1.1 g of the title compound as a white solid melting at 79-8 ° C. The structure is confirmed by H-NMR and mass spectrometry.

Example XXXTTT

20 Preparation of 5-trifluoromethvl-2-r 2-hvdroxv-4- (3-butoxv-2-hvdroxv-propoxv) fenvll-2H-benzotriazole

A mixture of 2.3 g of 5 "trifluoromethyl-2- (2,4-dihydroxyphenyl) -2H-benzotriazole, prepared in Example XXXI, 1.3 ml of butylglycidyl ether and 100 mg of ethyltriphenylphosphonium bromide in 50 ml of xylene is stirred for 14 hours under nitrogen refluxed Water (25 ml) and 25 ml ethyl acetate are added and 3 g of crude product is isolated.

Recrystallization from heptane gives 2.1 g of the title compound. 30, the structure of which is confirmed by NMR.

Example XXXTV

Preparation of 5-Trifluoromethyl-2- (2-Hydroxv-4-aminophenyl) -2H-benzo-35 triazole

The title compound is prepared starting from 4-amino-3-nitrobenzo-trifluoride and 3-aminophenol according to the general procedures of Example 1 and Example XXIX. The structure of the product is confirmed by NMR.

Example XXXV

5

Preparation of 5-trifluoromethyl-2-Γ-2-hvroxv-4- (2-ethylhexanovyl-amino) fenvll-2H-benzotria2ole

To a mixture of 4 g of 5-tifluoromethyl-2- (2-hydroxy-4-amino-10-phenyl) -2H-benzotriazole and 1.4 g of triethylamine in 75 ml of toluene is added dropwise a mixture of 2-ethylhexanoyl chloride in 125 ml of toluene added. The resulting mixture is treated with 100 ml of water and the crude product formed is purified by column chromatography to obtain 1.9 g of the title compound, which melts at 179-118 ° C. The structure is confirmed by NMR.

Example XXXVI

Preparation of 5-carbomethoxy-2- (2-hvdroxv-3-q-cumvl-5-tert-octyl-phenyl) -2H-benzotriazole a) Esterification of 4-amino-3-nitrobenzoic acid

700 ml of methanol, 20 g of xylene, 14 g of concentrated sulfuric acid and 100 g of 4-amino-3-nitrobenzoic acid are added to a 2 1 three-necked flask equipped with a mechanical stirrer. The solution is refluxed for 33 hours. The mixture is cooled to 35 ° C and neutralized to pH 7.8 · Water (1L) is added and the solid is collected and washed with 500ml, leaving 100.9g of methyl-4- overnight amino 3-nitrobenzoate is obtained.

b) Diazotization of methyl 4-amino-3-nitrobenzoate 35 To a 1 L three-necked flask equipped with a mechanical stirrer, 177 g of 96 # sulfuric acid and then slowly added 11 g of sodium nitrite over 90 minutes. The mixture is heated to 30 ° C to start the reaction. The temperature is kept below 70 ° C for 1 7 A 7 0 49. The mixture is then cooled to 15 ° C and 30 g of methyl 1-amino-3-nitrobenzoate is added over two hours, keeping the temperature between 15-20 ° C. The mixture is cooled to 0 ° C and 200 g of ice is added to make the solution suitable for the coupling reaction to form the monoazo compound.

c) Monoazo reagent 10 To a 2 1 three-necked flask equipped with a mechanical stirrer and an additional funnel, 52 g of 2-α-cumyl-4-tert-octyl-phenol, 20 g of water, 315 g of methanol, 7 g of xylene and 150 g of sodium hydroxide are added. The mixture is cooled to ~ 5 ° C and the diazonium salt solution prepared in step b is added over two hours under cooling to keep the temperature low than 3 ° C. After the diazonium salt solution is added, the pH is adjusted to 6.5 "7.0. The mixture is poured into 500 ml xylene and washed three times with water at 60CC. Xylene is removed by distillation to obtain 186 g of the monoazo reagent containing residual xylene.

d) Reduction of the monoazo reagent

186 g of the mono-reagent prepared in step c, 125 g of 2-butanol and 1.7 g of 2,3-dichloro-1,4-naphthoquinone are added to a 500 ml flask equipped with a mechanical stirrer. added. The mixture is heated to 90 ° C and then the resulting solution is placed in the addition funnel of a separate flask. 175 g of 2-butanol and 18.6 g of sodium hydroxide are placed in the second flask. The flask is heated to 95 ° C and the monoazo solution is added over two hours while distilling methyl ethyl ketone and 2-butanol. 2-Butanol (100 g) is added and azeotrope is distilled off. The mixture is then cooled and 300 g of xylene and 200 ml of water are added. The pH is adjusted to 7-7.5 with 20% sulfuric acid. The aqueous phase is separated at 60 ° C and the organic phase is washed twice with 200 ml of water. Xylene is removed by distillation and the residue formed is crystallized from methanol to give 8.8 g of the title compound, which melts at 1 0 0 7 4 7 0 50 at milkyc.

Example XXXVIT

5 Preparation of 5-ΓN.N-di-n-butylcarbaniovl-2-f2-hvdroxv - - - Q-cumvl-t: i-tert-octvl) fenvll-2H-benzotriazole a) Saponification of 5-carbomethoxy-2- (2-hydroxy-3-a-cumyl-5-tert-octyl-phenyl) -2H-benzotriazole 10

To a 250 ml three neck flask equipped with a mechanical stirrer, a thermometer, a condenser and a nitrogen feed, 1.8 g of potassium hydroxide and kO ml of methanol are added. The mixture is heated to 40 ° C to dissolve the potassium 15 hydroxide. Pound this solution into 2.7 g of 5-carbomethoxy-2- (2-hydroxy-3-alpha-cumyl-5-tert-octylphenyl) -2H-benzotriazole. prepared in Example XXXVI, added in ml0 ml of methanol. The reaction mixture is refluxed for six hours. The mixture is then cooled and acidified with hydrochloric acid. Ether and ethyl-20 acetate are added and the organic layer is separated and dried over anhydrous sodium sulfate. After vacuum stripping the solvent, 2.5 g of 5-carboxy-2- (2-hydroxy-3-a-cumyl-5-tert-octyl-phenyl) -2H-benzotriazole is isolated.

B) 5-chlorocarbonyl-2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzotriazole 2.5 g 5-carboxy-2- (2-hydroxy-3 ~ Q-cumyl) 5-tert-octylphenyl) -2H-benzotriazole, prepared in step a, is placed in a 250 ml flask equipped with a stirrer, a thermometer, a reflux condenser, a Dean-Stark trap and a nitrogen supply , brought. Toluene (100 ml) is added and the mixture is refluxed to remove trace amounts of water. The mixture is then cooled and 0.76 g of oxalyl chloride in 15 ml of toluene is added. The reaction mixture is slowly heated to 60 ° C and held at 60-65 ° C for eight hours until all hydrochloric acid is removed to yield the title compound as acid chloride.

1 0 07 47 0 51 c) 5- [N, N-di-n-butylcarbamoyl-2- (2-hydroxy-3-a-cumyl-5-tert-octyl) -phenyl] -2H-benzotriazole

0.8 g of di-n-butylamine, 6 ml of pyridine and 25 ml of toluene are added to a 500 ml flask equipped with a mechanical stirrer, a drying tube, a thermometer and a dropping funnel. The mixture is cooled to 0 ° C and the acid chloride solution prepared in step b is placed in the dropping funnel and added to the reaction mixture at ~ 5 ° C to -10 ° C over a period of 30 minutes. The reaction mixture is stirred at that temperature for 1.5 hours and then kept at ambient temperature overnight. The mixture was filtered and then vacuum stripped to give 3.0 g of a crude solid. The solid product is chromatographed to yield 1.2 g of the title compound as a tan brown solid melting at 131-15133 ° C. The structure is confirmed by NMR and mass spectrometry m / z 596.

Example Ι1Ι 20 5-trifluoromethvl-2- (2-hvdroxv-5-tert-octvlfenvl) -2H-benzotriazole

The title compound is prepared from the diazo compound of 4-amino-3-nitrobenzotrifluoride and 1-tert-octylphenol according to the general procedure of Example I and is purified by silica gel chromatography. Recrystallization of the product from either heptane or methanol gives the title compound as an almost white solid melting at 80-8 ° C.

Application example XXXIX 30

To determine the effect on thermal durability and loss rate from a high solids thermosetting acrylic lacquer of various 2H-benzotriazole UV absorbers substituted with a variety of electron withdrawing groups and electron donor groups, the following tests executed .

A high solids thermosetting clear acrylic lacquer is prepared by mixing an experimental acrylic polyol lacquer and hexamethoxymethylraelamine (Resimené® 7 ^ 7, Monsanto) at a solid ratio of 60/0. The dodecylbenzene sulfonic acid catalyst (Nacuré® 5225; King Industries) is added in an amount of 0.70% by weight. To form a model system of the acrylic melamine resin, the flow aid Modaflow® (Monsanto) is added in an amount of 0.25% by weight.

The clear model lacquer is reduced with xylene using a Zahn # 2 head to a viscosity of 26-27 seconds and applied to a 2.5 ^ 4 cm quartz glass 10 x 7.62 cm using a conventional air spray at 3.5 kg / cm2. Harden by baking the slide at 127 ° C for 30 minutes. The clearcoat is stabilized with 1% by weight of a sterically hindered amine light stabilizer, bis (1-octyloxy-2,2,6,6-tetramethylpiperidine-1-yl) sebacate, (TINUVIMiv 123, Ciba-Geigy). The various benzotriazole UV absorbers to be tested are included in the clearcoat in an amount of 5% by weight. The film thickness on the quartz glass slides ranges from 0.029 to 0.036 mm.

The films on the quartz slides are weathered according to the following conditions in a Xenon Arc Weather-Ometer with controlled irradiation at 6500 W using an internal quartz-20 filter and an external borosilicate S-type filter. The irradiation cycle is as follows: ^ 0 minutes of ordinary irradiation without water spraying, followed by 20 minutes of light plus front spraying, followed by 60 minutes of light irradiation and finally 6 hours of dark plus rear spraying (condensation). The setting is 0.55 W / m2 at 3 ^ 0 nm, 1.98 kJ / h. In the light cycle, the temperature of the black panel is controlled at 70 ± 2 ° C. The relative humidity in the light cycle is in the range of 50-55% and in the dark cycle is 100%. The absorption of the long wavelength UV band as a function of the number of hours of weathering with a Xenon are is shown in the table below.

To monitor the loss of the UV absorbers from the clearcoats, UV spectra are measured initially and at regular intervals after weathering. The UV spectrophotometer measures absorbance linearly to 5> 5 absorbance units using a reference 35 beam attenuation technique.

The degradation products of the UV absorber are believed not to contribute to the UV spectrum. This is tested by following the ratio of the absorbance of the band at about 300 nm and the band at about 340 nm. The ratio does not change during the weathering of the sample. This suggests that the UV spectrum of the weathered films corresponds to the amount of UV absorber remaining in the film, with very little or no contribution of the degradation products formed under the influence of light to the spectrum.

The data in the table below is based on Structural Formula A after 1211 hours of exposure of the clearcoats containing the Benzotriazole UV absorbers to be tested.

10 -----

Compound Units ab- G2 R: R2 sorption loss A 1.7982 hydrogen -P0 (0Et) 2-tert-octvl 15 -----: - B 1,6300 hydrogen nitro tert-octyl C 1.4863 phenyl-S-tert -butyl -CH2-CH2C00C8H17 20 D 1,4002 hydrogen hydrogen —CH2-CH2 C00CH-, E 1,1872 methoxy tert-butyl methyl F 0.3259 hydrogen tert-butyl -CH -.- ChhCOOCH ^ 25 ----- G 0.4527 hydrogen hydrogen a-cumyl H 0.4420 hydrogen tert-butyl -CH2-CH2C00CeH; - 30 I 0.4299 hydrogen tert-octyl a-cumyl J 0.4134 hydrogen hydrogen tert-octyl K 0.3777 hydrogen tert -octvl tert-octvl 35 -----

L 0.3712 hydrogen tert-butyl -CH2CH2CH2OH

M 0.3433 hydrogen α-cumyl -CH2-CH2C00CH3 40 N 0.3098 cyan tert-butyl tert-butyl 0 0.2689 phenyl-S02- tert-butyl -CH2-CH2C00C6H, - P 0.2576 hydrogen α-cumyl a -cumyl 45 ----- Q 0.2492 hydrogen α-cumyl tert-octyl

Consideration of these data leads to some clear conclusions regarding the photostability of 2H-benzotriazole-UV-50 absorbents and the nature of the substitution affecting that photostability.

1 0 0 7 470

Greater photostability occurs when Rj is α-cumyl or phenyl and when G2 is an electron withdrawing group, such as phenylsulfonyl or cyano.

The nature of the group R2 has less influence on the photostability of the benzotriazole UV absorbers.

From these observations, an idealized benzotriazole UV absorber can theoretically be designed, where G2 is an electron withdrawing group, R is an effective bulky group, and R2 is a thermally stable group. Such an idealized compound can be a benzotriazole, wherein G 2 is phenylsulfonyl, R 1 is α-cumyl and R 2 is tert-octyl. This benzotriazole is generically claimed in U.S. Patent 5,280,112. The data given in Example XL below confirms this prediction and this "idealized" compound does indeed exhibit a very low loss rate, which is much lower than in the prior art.

Example XL

According to the general procedure of Example XXXIX, a number of additional benzotriazole compounds to be tested are obtained in concentrations between 1.93 and 3% by weight, such that equal molar concentrations of the benzotriazole to be tested are obtained in an equal film thickness, and sufficient for obtaining an initial absorption of about 2.0 absorption units, incorporated into a high-solids acrylic melamine resin.

The test disks are exposed at X180 cycles (0.4p Watt / m'O in a Xe-non-Arc Weather-Ometer. Initial UV absorption is measured, followed by measurements at approximately 250 hour intervals during the first 2000 hours and then every 500 hours Each clear coat also contains 1 wt% of a sterically hindered amine light stabilizer, bis (1-octyloxy-2,2,6,6-tetramethylpiperidine-yl) sebacate.

The data in the table below is based on compounds of the formula A after 1253 hours of exposure of the clearcoats containing the benzotriazole UV absorbers to be tested.

1007470 55

Compound Units ab- G2 Rj R2 sorption loss 5 H 0.2929 hydrogen phenyl a-cumyl Q 0.2351 hydrogen a-cumyl tert-octyl S 0.1271 CF3 a-cumyl tert-octyl 10 ----- T 0.1827 phenyl-SO2 tert-butyl tert-butyl

The data in the table below is based on compounds of the formula A after 1989 hours of exposure of the clearcoats containing the benzotriazole UV absorbers to be tested.

Compound Units ab- G2 Rj R2 sorption loss 20 R 0.3729 hydrogen phenyl a-cumyl Q 0.287 hydrogen α-cumyl tert-octyl S 0.1597 CF3 a-cumvl tert-octyl 25 ----- T 0.2659 phenyl- SO 2 tert-butyl tert-butyl

The data in the table below is based on compounds of formula A after 2521 hours of exposure of the clearcoats containing the benzotriazole UV absorbers to be tested.

Compound Units ab- G2 Rj R2 loss of sorption 35 R 0.9829 hydrogen phenyl a-cumyl Q 0.9059 hydrogen α-cumyl tert-octyl S 0.2192 CF, a-cumyl tert-octyl 90 ------- T 0.3570 phenyl-SO2 tert-butyl tert-butyl

The above three tables show that compound S and especially compound T, which contain an electron withdrawing group at the 5-95 site of the benzo ring, are significantly more durable than benzotriazoles that do not have such a group at the benzo ring.

The data in the table below is based on compounds of the formula A after 1269 hours of exposure of the clearcoats containing the benzotriazole UV absorbers to be tested.

7 4 7 0 56

Compound Units ab- G2 Rj R2 sorption loss 5 Q 0.2293 hydrogen α-cumyl tert-octyl S 0.0921 CF3 α-cumyl tert-octyl T 0.1965 phenyl-S02 tert-butyl tert-butyl 10 ----- U 0 .0944 phenyl-S02 a-cumyl tert-octyl V 0.1719 chlorine a-cumyl tert-octyl 15 W 0.1655 fluorine a-cumyl tert-octyl X 0.1796 hydrogen phenyl tert-octyl

The data in the table below is based on compounds of the formula A after 1518 hours of exposure of the clearcoats containing the benzotriazole UV absorbers to be tested.

Compound Units ab- G2 Rj R2 sorption loss 25 ----- Q 0.2662 hydrogen α-cumyl tert-octyl S 0.1116 CF-, α-cumyl tert-octyl 30 T 0.2423 phenyl-S02 tert-butyl tert -butyl U 0,1114 phenyl-S02 a-cumyl tert-octyl V 0,1955 chlorine a-cumyl tert-octyl 35 ----- W 0,168 fluoro a-cumyl tert-octyl X 0.2220 hydrogen phenyl tert Octyl 40 The data in these tables clearly show that benzotriazoles substituted at the benzo ring with an electron withdrawing group, especially one such as trifluoromethyl or phenylsulfonyl, are particularly durable, as evidenced by measurements of the low loss rate of absorption values after exposure to actini-45 radiation. The connections S, U, V and W are particularly durable and comply with the profile proposed above. Indeed, the prediction that compound U would be particularly durable is confirmed by the above data. Consideration of the data for the compounds T and U shows the additional beneficial effect that these 50 contain an effective bulky group, such as α-cumyl, at the Rj-Si u / 4 7 0 57 site, compared to only one alkyl group such as tert -butyl in that place.

1 0 0 7 4 7 0

Claims (34)

A lacquer composition stabilized with a benzotriazole, which benzotriazole exhibits improved durability and a low loss rate when incorporated into the lacquer, which composition consists of (a) a resin selected from the group of a thermoset - the acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane-modified acrylic melamine, an acrylic resin with carbamate side groups cross-linked with melamine, or an acrylic polyol resin cross-linked with carbamate-containing melamine, and ( b) 0.01-5 w / w, based on solid resin particles, of a benzotriazole of the formula A, B, C or D 15 OH G / ^ / B 'XX / ν ~ λΤ w 20 N — 1 r2 OH ££> - & - R2 30 2 - G 0H - ch2ch2co-r5 1 0 0 7 A 7 0 OH OH 5 if ^ NN> - [ipL — f ^ SrK DT5i ©> Gi ^ V yCS R2 R2 10 15 in which G, G2 or T is an electron withdrawing group, G] is hydrogen or halogen, G2 is halogen, nitro, cyano, R3SO-, R3SCF-, -C00G ,, CF-, -P (0) (C6H.) 2, -CO-G3, -CO-NH-G- ,, -C0-N (G3) 2. -N (G3) -C0-G ,, 25 CO-I-G3 CO-I-G3 / / -N or -N \ \ coJ co-1 30, Gj is hydrogen, straight or branched alkyl with 1-2 ^ carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of ^ 12 carbon atoms, phenylalkyl of 7-15 carbon atoms, phenyl, or where the phenyl group or phenylalkyl group on the phenyl ring is substituted with 1A alkyl groups of 1-A carbon atoms, R 1 hydrogen, straight or branched chain alkyl of 1 to 2 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 * 12 carbon atoms, phenylalkyl of 7-15 carbon atoms, phenyl, or where 1 0 0 7 47 0 at the phenyl group or the phenylalkyl group at the phenyl ring is substituted with 1-4 alkyl groups of 1-4 carbon atoms, R2 straight or branched alkyl of 1-24 carbon atoms, straight or branched alkenyl of 2-18 carbon atoms, cycloalkyl of 5-12 carbon-5 atoms, phenylalkyl having 7-15 carbon atoms, is phenyl, or wherein the phenyl group or phenylalkyl group is attached to the phenyl ring substituted with 1-4 alkyl groups of 1-4 carbon atoms; or R2 is hydroxyl or -OR /, wherein R / is straight or branched chain alkyl of 1-24 carbon atoms; or wherein the alkyl group is substituted with one or more groups -OH, 10-OCO-R 1, -O-R / -NCO or -NH 2 or mixtures thereof; or wherein the alkyl group or the alkenyl group are interrupted by one or more groups -O-, -NH- or —NR /, - or mixtures thereof and which may be unsubstituted or substituted with one or more of the groups -OH, -OR /, or —NH2 or mixtures thereof; or R2 is -SR3, -NHR3 or -N (R3) 2; or R2 15 - (CH2) m -CO-X- (Z) p -Y-R]. wherein X is -O- or -N (R) t,) -, Y is -O- or -N (Rj-) -, Z is C2 -C12 alkylene or C1 / -C12 alkylene interrupted by a 20 to three nitrogen atoms, oxygen atoms or a mixture thereof, or C3-C12alkylene, butenylene, butynylene, cyclohexylene or phenylene, each of which is substituted with a hydroxyl group, m is zero, 1 or 2, p is 1, or p is also zero is when X and Y are -NiR ,,) - and 25 -N (R17) -, Rj- is a group -C0-C (R1g) = C (H) R] Q, or when Y is -N ( R1:) ~ together with R27 forms a group -CO-CH = CH-CO-, wherein R11 is hydrogen or methyl and Rig is hydrogen, methyl or -CO-X-R20, wherein R2Cl is hydrogen, C. -C, 2 is alkyl or a group of the formula 30 W, "\ ^ ~ ^ (CH2) -CO-X ~ (Z) - 35. p, wherein the symbols R2, R3, X, Z, m and p defined above 1 0 0 7 4 7 0 have meanings and R 18 and R 17 independently hydrogen, C 1 -C 1:? alkyl, C3-C12alkyl interrupted by 1 ~ 3 oxygen atoms or cyclohexyl or C7-C15 aralkyl and R16 together with R) 7 in case Z is ethylene, also forms ethylene, 5n is 1 or 2, if n 1, R5 is Cl, 0Rt or NR7R8 or R5 is -P0 (0R12) 2, -OSi (Rn) 2 or -0C0 -Rn, or straight or branched C1 -C21 alkyl, which is interrupted by -0-, -S-or -NRjj, and which may be unsubstituted or substituted with -OH or -CO-Rn, C 1 -C 12 cycloalkyl, which is unsubstituted or substituted with -OH, straight or branched C 2 -C 18 alkenyl, which is unsubstituted or is substituted with -OH, C 1 -C 13 aralkyl, -CH 2 -CHOH-R .. or is glycidyl, ^ i. R 6 is hydrogen, straight or branched C 1 -C 12 alkyl, which is unsubstituted or substituted with one or more groups OH, OR 2, or NH 2, or is —0RÉ - (0CH2CH2) kOH or - (0CH2CH2) wOR2. where w is 1-12 and R2. alkyl of 1-12 carbon atoms, R7 and Rg are independently hydrogen, alkyl of 1-18 carbon atoms, straight or branched C3 -C18 alkyl interrupted by -0-, -S- or 20 -NRn-, C-C12 cycloalkyl, Ct, -ClJ; aryl or C 1 -C 3 hydroxyalkyl, or Ηβη Rg together with the N atom are a pyrrolidine, piperidine, piperazine or morpholination, when n is 2, Rg is one of the divalent groups —0 — Rg-0- or - N (R1;) is R10-N (RU). Rg C 2 -C 6 alkylene, Cg-Cg alkenylene, C 1 -alkynylene, cyclohexylene. straight or branched C 1 -C 4 alkylene interrupted by -O- or by —CH 2 —CH 2 H — CH 2 —0 — R 1 g — 0 — CH 2 —CH 2 H —CH 2 -, R 10 is straight or branched C 2 -C 12 alkylene . which may be interrupted by -0-, cyclohexylene or 3 ° - or 35 - 1 h 0 7 4 7 o or R10 and Ru form a piperazine ring with the two nitrogen atoms, Rj / 4 straight or branched C2-C8 alkylene or straight or branched 02-0Κ) alkylene interrupted by -0-, cycloalkylene, arylene or 5. CH 3 -Ol-O-j CH, ch 3 'tO-KD- * ch 3 15, wherein R 7 and R 9 are independently hydrogen or alkyl of 1-18 carbon atoms or R- and Rfc together are alkylene of 4 -6 carbon atoms, 3-oxapentamethylene, 3 "iminopentamethylene or 3-methyliniinopenta-methylene are, R 1] hydrogen, straight or branched C 1 -C 6 alkyl, C 1 -C 12 cycloalkyl, straight or branched C 1 -C 8 alkenyl, C 1-6 -ClU aryl or C7-C17j aralkyl, R12 is straight or branched Cj-Cl8 alkyl, straight or branched 03-0ιε alkenyl, C5-C10 cycloalkyl, C6-Cl6 aryl or C7-C13 aralkyl, Rj3 H, straight or branched C -C 18 alkyl substituted with -P0 (OR 12) 2 phenyl which is unsubstituted or substituted with OH, C 7 -C 18 aralkyl or -CH 2 OR 2, R 3 alkyl of 1-20 carbon atoms hydroxyalkyl of 2-20 carbon atoms, alkenyl of 3 ~ 18 carbon atoms, cycloalkyl of 5-12 carbon atoms, phenylalkyl of 7-15 carbon atoms, aryl of 6-10 carbon atoms or wherein the aryl is substituted with one or two alkyl groups of 1- 4 carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl, where the perfluoroalkyl group has 6-16 carbon atoms, L is alkylene of 1-12 carbon atoms, alkylidene of 2-12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene and T-SO -, —S02—, -S0-E-S0-, -S02-E-S02-, -C0-, -CO-E-CO-, 35 -COO-E-OCO-, -CO-NG3-E-NG -CO- or -NG3-CO-E-CO-NG3- where E is alkylene with 2-12 carbon atoms, cycloalkylene with 5 "12 carbon atoms or alkylene, interrupted or terminated with cyclohexylene of 8-12 carbon atoms, is 1007470 which benzotriazole exhibits improved durability and low loss rate values when the lacquer is exposed to actinic radiation, as evidenced by a loss of less than 0, 22 absorbent units after exposure for 1200 hours or less than 0.27 absorbent units after exposure for 1500 hours or less than 0.40 absorbent units after exposure for 2500 hours in a Xenon-Arc Weather-OMeter. 2. A composition according to claim 1, wherein component (b) is a compound of the formula A 'N ° H "XXhn" "er N 20 wherein G2 is fluorine, chlorine, cyano, R3S0v_, CF ·, -, -C0-G · -C00-G, or -C0-N (G3) 2, G3 is alkyl of 1-12 carbon atoms, R 1 is hydrogen, alkyl of 1-12 carbon atoms, phenyl or phenylalkyl of 7-15 carbon atoms, or phenyl or phenylalkyl which is substituted on the phenyl ring with 1 or 2 alkyl groups of 1 to 4 carbon atoms, R 2 alkyl of 1 to 12 carbon atoms, phenyl, phenylalkyl of 7 to 15 carbon atoms or -CH 2 CH 2 COG /, where Gh is hydrogen or alkyl of 1-24 carbon atoms or wherein the alkyl group is substituted with 30 OH, is interrupted by one to six -0 atoms or is both substituted with OH and interrupted by one to -0 -0 atoms, and R 1 is alkyl of 1-18 carbon atoms or aryl of 6-10 carbon atoms or the aryl group is substituted with one or two alkyl groups of 1-4 carbon atoms. 35 The composition of claim 2, wherein in the compound of formula A 'G2 is fluorine, chlorine, cyano, R3SO2, CF3, -C00-G3 or -C0-N (G1) 2, 7 7 7 0 G3 alkyl of 1 to 8 carbon atoms, R 1 hydrogen, phenyl or α-cumyl, R 2 alkyl of 4-12 carbon atoms or phenyl and R 3 phenyl or alkyl of 8-12 carbon atoms. 5 The composition of claim 3. wherein G 2 is phenyl-SO 2, octyl-SO 2, fluoro or CF -, - R 1 is α-cutnyl or phenyl and R is t-butyl or t-octyl. 10 The composition of claim 1, wherein component (a) is a thermosetting acrylic melamine resin or an urethane acrylic resin. The composition of claim 1, additionally containing a stabilizing amount of a phenolic antioxidant selected from the group of n-octadecyl-3,5 "di-tert-butyl-4-hydroxyhydrocinnamate, neopentaantetrayl-tetrakis ( 3,5-di-tert-butyl-4-hydroxyhydrocinnamate), di-n-octadecyl-3-5-di-tert-butyl-4-hydroxybenzyl-20 phosphonate, 1,3,5-tris (3.5 ~ di- tert-butyl-4-hydroxybenzyl) isocyanurate, thiodiethylene bis (3.5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3.5 ”trimethyl-2,4,6-tris (3,5” di-tert-butyl 4-hydroxybenzyl) benzene, 3,6-dioxaoctamethylene bis (3-methyl-5-tert-hutyl-4-hydroxyhydrocinnamate). 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 1,3.5 "tris (2,6-dimethyl-4 -tert-butyl-3-hydroxybenzyl) isocyanurate, 1,1,3-tris (2-methyl-4-hydroxy-5 "tetr-butylphenyl) butane, 1,3,5 * tris [2- (3.5" di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl] isocyanurate, 3.5 ”di (3.5” di-tert-butyl-4-hydroxybenzyl) mesitol, hexamethylene bis (3,5 ~ di-tert-butyl-4-hydroxyhydrocinnamate) 1- (3, 5-di-tert-butyl-4-hydroxyanilino) -3,5 ”di (octylthio) -s-triazine, N, N'-hexamethylene bis (3.5” di-tert-butyl- 4-hydroxyhydrocinnamamide), calcium bis (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis [3, 3 ”di (3” tert-butyl-4-hydroxyphenyl) butyrate], octyl-3 .5 "di-tert-butyl-4-hydroxybenzyl mercaptoacetate, bis (3,5-di-tert-butyl-4-hydroxyhydro-35-cinnamoyl) hydrazide and N, N'-bis [2- (3.5" di-tert- butyl-4-hydroxyhydro-cinnamoyloxy) ethyl ioxamide. The composition of claim 6, wherein the phenolic anti-tw ϋ / 4 7 0 oxidant neopentaantetrayl-tetrakis (3.5 "di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl-3,5-di-tert- butyl-4-hydroxyhydrocinnamate, 1.3.5 "trimethyl-2,4,6-tris (3.5" di-ter t-buty 1-4-hydroxy benzyl) benzene, 1,3,5-tris (3,5-di-tert -butyl-4-hydroxybenzyl) isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene bis (4,6-di-tert-butylphenol). The composition of claim 1, additionally containing an effective stabilizing amount of a sterically hindered amine selected from the group of 10 bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1, 2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di (1,2,2,6,6-pentamethylpiperidin-4-yl) - (3,5 "di-tert-butyl-4-hydroxy- benzyl) butyl malonate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearoyl-2,2,6,6-tetra-15 methylpiperidine, 3-n-octyl-7,7.9.9 ”tetramethyl-1 , 3,8-triaza-spiro [4.5] decane-2,4-dione, tris (2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, 1,2-bis (2,2,6,6-tetramethyl-3-oxopiperazine -4-yl) ethane, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro [5.1.11.2] heneicosan, the polycondensation product of 2,4-dichloro-6-tert-octylamino -s-triazine and 4,4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine), the polycondensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 4 , 4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine) and 1,2-25 dibromoethane, tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) -1,2,3,4-butane tetra -carboxylate, tetrakis (1,2,2,6,6-pentamethylpiperidin-4-yl) -1,2,3,4-butane tetra-carboxylate, the polycondensation product of 2,4-dichloro-6-morpholino-s- triazine and 4,4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine), N, N ', N ”, N'” tetrakis [(4,6-bis (butyl-1,2,2) 6,6-pentamethylpipendin-4-yl) amino-s-triazin-2-yl] -1,110-diamino-4,7-diazadecane, mixed [2,2,6,6-tetramethylpiperidin-4-yl / {J, β, β'β'-tetramethyl-3,9 "35 (2,4,8,10-tetraoxaspiro [5.5] undecane) diethy1] -1,2,3,4-butane tetracarboxylate, mixed [1,2 2,6,6-pentamethylpiperidin-4-y1 / β, β, β'β'-tetramethyl-3,9 "(2,4,8,10-tetraoxaspiro [5] undecane) diethyl] -1, 2,3,4-but tetra-1 0 7 47 0 carboxylate, octamethylene bis (2,2,6,6-tetramethylpiperidine-4-carboxylate), 4,4-ethylene bis (2,2,6,6 -tetramethylpiperazin-3-one), N-2,2,6,6-tetra- methylpiperidin-4-yl-n-dodecylsuccinimide, Nl, 2,2,6,6-pentamethyl-5-piperidin-4-yl-n-dodecylsuccinimide, Nl-acetyl-2,2,6,6-tetramethyl-piperidin-4 -yl-n-dodecylsuccinimide, 1-acetyl-3-dodecyl-7,7.9.9 "tetramethyl-1,3,8-triazaspiro [4.5] dec-2,4-dione, di (1-octyloxy-2.2.6.6- tetramethylpiperidin-4-yl) sebacate, di (1-cyclohexyloxy-2,2.6,6-tetramethylpiperidin-4-yl) succinate. 1-octylox-2,2,6,6-10 tetramethyl-4-hydroxypiperidine, poly {[6-tert-octylamino-s-triazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2, 6,6-tetramethylpiperidin-4-yl} imino-hexamethylene [4- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -imino] and 2,4,6-tris [N- ( 1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -n-butylamino] -s-triazine. The composition of claim 8, wherein the sterically hindered amine bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis- (1,2,6,6,6-pentamethylpiperidin-4-yl) sebacate , di (1,2,2,6,6-penta-methylpiperidin-4-yl) - (3,5-di-tert-butyl-4-hydroxybenzyl) butyl malonate, the polycondensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexa-methylenebis (amino-2,2 , 6,6-tetramethylpiperidine), N, N ', N ", N'" - tetrakis [(4,6-bis (butyl (1,2,2,6,6-pentamethylpiperidin-4-yl) amino) ) -s-tri-25 azin-2-yl] -1,110-diamino-4,7-diazadecane, di (1-octyloxy-2,2,6,6-tetra-methylpiperidin-4-yl) sebacate, di ( 1-cyclohexyloxy-2,2,6,6-tetra-methylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, poly {[6-tert-octylamino-s -triazin-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) iminohexamethylene [4-30 (1-cyclohexyloxy-2,2,6,6-tetrameth) ylpiperidin-4-yl) iinino] or 2,4,6-tris [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -n-butyl-amino] -s-triazine . 10. A composition according to claim 1, additionally comprising another UV absorber selected from the group of the s-triazines, the oxanilides, the hydroxybenzophenones, the benzoates and the α-cyanoacrylates. 1 0 0 7 A 7 0 The composition of claim 10, wherein the composition additionally contains a s-triazine containing 2,4-bis (2-dimethylphenyl) -6- (hydroxy-1-octyloxyphenyl) s-triazine; 2,2'-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -s-triazine; 2,4-bis (2,2,5-dimethylphenyl) -6- [2-hydroxy - ^ - (3-do- / tridecyloxy-2-hydroxypropoxy} -phenyl] -s-triazine; or 2- (2-hydroxy) ethyl amino) -4,6-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-1-yl) amino] -s-triazine. 12. A compound of the formula I, II, III or IV OH G \ ^ J J ^ xxycf. Ez 20 OH T E J 2 30 G, 0 \ - - CH2CH2CO-E5 35 n 1007470 G, OH OH / Gl \ E "10 wherein Gj is hydrogen or halogen, G2 cyano, E3S0-, E3S02-. -C00G3. CF? -. -P (0) (CbH5) 2. -C0-G., -CO-NHG3 or -C0-N (G1) 2, G3 is straight or branched alkyl of 1-2 * 4 carbon atoms, straight or branched alkenyl of 2-18 carbon atoms, cycloalkyl with 5-12 carbon atoms, phenylalkyl having 7-15 carbon atoms, is phenyl, or where the phenyl group or phenylalkyl group on the phenyl ring is substituted with 1-4 alkyl groups having 1-4 carbon atoms, Ej hydrogen, phenylalkyl having 7-15 carbon atoms, or phenyl, or wherein the phenyl group or phenylalkyl group on the phenyl ring is substituted with 1-4 alkyl groups of 1-4 carbon atoms, E2 straight or branched alkyl of 1-24 carbon atoms, straight or branched alkenyl of 2-18 carbon atoms, cycloalkyl of 5-12 carbon atoms, phenylalkyl having 7 * 15 carbon atoms, is phenyl, or wherein the phenyl group or phenylalkyl group on the phenyl ring is substituted with 1-3 alkyl groups having 1-4 carbon atoms; or E2 hydroxyl or -0E ;. is. wherein E <is straight or branched chain alkyl of 1-24 carbon atoms; or wherein the alkyl group is substituted with one or more groups -OH. -0C0-En, -0E4, -NCO or -NH-. or mixtures thereof; or wherein the alkyl-30 group or the alkenyl group are interrupted by one or more groups -O-, —NH— or —NEi, - or mixtures thereof and which may be unsubstituted or substituted with one or more of the groups —OH -OE4 or -NH2 or mixtures thereof; or E2 is -SE3, -NHE3 or -N (E3) 2; or E2 - {CH2) nr CO-X- (Z) -Y-Eib 35. where X is -0- or -N (El6) -. Y is -O- or -N (E17) -, Z is C2 -C12 alkylene or C1 -C12 alkylene interrupted by a 1. O7 is 470 to three nitrogen atoms, oxygen atoms or a mixture thereof, or C3 -C12 alkylene, butenylene, butynylene, cyclohexylene or phenylene, each of which is substituted with a hydroxyl group, m is zero, 1 or 2, 5 p is 1 , whether p is also zero if X and Y are -N (Elt) - and -N (E17) -, E1, respectively; a group -C0-C (Elg) = C (H) E19, or when Y is -N (E1?) - together with E17 forms a group -C0 ~ CH = CH-C0-, wherein Elg is hydrogen or methyl and E19 is hydrogen, methyl, or -CO-X-E20, wherein E20 is hydrogen, C5 -C12 alkyl 10, or a group of the formula * OH \ R G2 N vzr— / ^ (CH2) -CO-X— ( 2) - m 'p, wherein the symbols E ,, G2, X, Z, m and p having the meanings defined above and Ε; έ and EJT independently of each other are hydrogen, C 1 -C 6 alkyl, C3-C) 2 is alkyl interrupted by 1-3 oxygen atoms or cyclohexyl or C7 -C13 aralkyl and E; t together with E, - in case Z is ethylene, also forms ethylene, η is 1 or 2, 2p if η is 1 E- Cl is 0E6 or NE7Eg or E- -P0 (0E12) 2 is —OSi (En} 3 or -0C0-E ;,), or straight or branched C 1 -C 2 alkyl, interrupted by -0- -S-or -NEn and which may be unsubstituted or substituted with -OH or -OCO-E5., Cb-Cl2 cycloalkyl, which is unsubstituted or -substituted with -OH, straight or branched C2-C16 alkenyl, that unsong is substituted or substituted with -OH, C 1 -C 18 aralkyl, -CH 2 -CHOH-E; or is glycidyl, EÊ is hydrogen, straight or branched C 1 -C 24 alkyl, which is unsubstituted or substituted with one or more groups OH, OE 1, or NH :, or is 35 -0E6 - (0CH2CH2) wOH or - ( OCH2CH2) w0E21, where w is 1-12 and E2) is alkyl of 1-12 carbon atoms, E7 and Eg is independently hydrogen, alkyl of 1-18 carbon atoms, straight or branched C3-C18 alkyl interrupted by -0 -, -S- or iuv / 4 7 0 -NEn-, C 1 -C 12 cycloalkyl, C 1 -C 18 aryl or C 1 -C 3 hydroxyalkyl, or E; and Ee together with the N atom are a pyrrolidine, piperidine, piperazine or morpholination, if n is 2, E5 is one of the divalent groups -0-E9 ~ 0- or 5 ~ Ν (Εη) -Ε10-Ν (Εη) - is. E9 C 2 -C 8 alkylene, C 1 -C & alkenylene, C 1 -alkynylene, cyclohexylene, straight or branched C 1 -C 10 alkylene, interrupted by -O- or by —CH 2 -CHOH-CH 2 -O-1-O-0- CH2-CH0H-CH2-, E10 is straight or branched C2 -C12 alkylene, which may be interrupted by -O-, cyclohexylene or ~ 20 ~ 20 or E1C and And with the two nitrogen atoms form a piperazine ring, El9 straight or branched C 2 -C 8 alkylene or straight or branched C 1 -C 10 alkylene interrupted by -O-, cycloalkylene, arylene or 25 CH 3 CH 3 30 CH 3 _ ch 3 35, wherein E7 and Eg are independently hydrogen or alkyl of 1- 18 carbon atoms are either E? And Ee taken together as alkylene having 4-6 carbon atoms, 3 "oxapentamethylene, 3" iinopentamethylene or 3 'ethyliminopenta- methylene, and hydrogen, straight or branched C 1 ~ C 1-8 alkyl, C 5 -C 12 cycloalkyl, straight or branched C 3 -C 8 alkenyl, C 8 -C 11 aryl or C 7 -C 15 aralkyl, E 12 straight or branched C 1 -C 8 alkyl, straight or branched C 3 -C 8 alkenyl, 5 C 5 -C 10 cycloalkyl , C6 -C16 aryl or C7 -C15 aralkyl, Ej3H, straight or branched C1 -C18 alkyl, which is substituted with -P0 (0E12) 2, phenyl, which is unsubstituted or is substituted with OH, C7 -C15 aralkyl or -CH20E12, E3 alkyl of 1-20 carbon atoms, hydroxyalkyl of 2-20 carbon-10 atoms, alkenyl of 3 ~ 18 carbon atoms, cycloalkyl of 5 ~ 12 carbon atoms, phenylalkyl of 7-15 carbon atoms, aryl of 6-10 carbon atoms or aryl is substituted with one or two alkyl groups of 1 to 1 carbon atoms, or 1,1,2,2-tetrahydroperfluoroalkyl, where the perfluoroalkyl group has 6 to 16 carbon atoms, 15. alkylene of 1-12 carbon atoms, alkylidene of 2 -12 carbon atom, benzylidene, p-xylylene or cycloalkylidene and T is -S0-, -S02-, -S0-E-S0-, -so2-e-so2-, -co-, -co-e -co-, -C00-E-0C0- or -CO-NGr-E-NG -— CO-, where E is alkylene of 2-12 carbon atoms, cycloalkylene of 5-12 carbon atoms, or alkylene interrupted by or terminated with cyclohexylene of 8-12 carbon atoms, i s, G-G-, or hydrogen, with the proviso that Ej is not phenylalkyl when G2 is E3SO- or E3SO2. 25 A compound according to claim 12, which is a compound of the formula I 'OH 3 ° f-γ V 35 wherein G2 is cyano, E3S02-, CF3-, -C00-G3, -C0-NHG3 or -C0-N (G3 ) Is 2, 1007470 is G3 alkyl of 1-12 carbon atoms, Ej is hydrogen, phenyl or phenylalkyl of 7 * 15 carbon atoms, or the phenyl or phenylalkyl group on the phenyl ring is substituted with 1 or 2 alkyl groups of 1-¾ carbon atoms, 5 is E2 alkyl of 1-12 carbon atoms, phenyl, phenylalkyl of 7-15 carbon atoms or -CH2CH2C00G (, wherein G /, is hydrogen or alkyl of 1-2¾ carbon atoms, the alkyl group being substituted with OH or interrupted by a up to six -0 atoms or both is substituted with OH and interrupted by one to six -0 atoms. 10 is E3 alkyl of 8-18 carbon atoms or aryl of 6-10 carbon atoms, or wherein the aryl group is substituted with one or two alkyl groups of 1-¾ carbon atoms with the proviso that E: is not phenylalkyl as G2 E3S0- or E3S02- is. 15 1¾. A compound according to claim 13, wherein G2 is cyano, E3SO2, CF3, -C0-G3 or -C0-N (G3) 2, G3 alkyl of 1-8 carbon atoms. Ej hydrogen, phenyl or α-cumyl. E2 alkyl having ¾-12 carbon atoms and E3 is phenyl or actyl, with the proviso that Wj is not α-cumyl not α-cumyl when G2 is E3SO2-. A compound according to claim 1¾. where G2 is CF3 ~, Ej is α-cumyl and E2 is tert-butyl or tert-octyl. A composition stabilized against thermal, oxidative or light-induced degradation, which consists of (a) an organic material subject to thermal, oxidative or light-induced degradation and (b) an effective stabilizing amount of a compound 35 of the formula I, II, III or IV according to claim 12. The composition of claim 16, wherein the organic material is a natural, semi-synthetic or synthetic polymer. 1 0 0 7 A 7 0 18. Composition according to claim 1 ?. the polymer being a thermoplastic polymer. 19. The composition of claim 18, wherein the polymer is a polyolefin or polycarbonate. The composition of claim 19. wherein the polymer is polyethylene or polypropylene. The composition of claim 20, wherein the polymer is polypropylene. 22. The composition of claim 16, wherein the organic material is a resin selected from the group consisting of a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane-modified acrylic melamine, an acrylic resin with carbamate side groups, cross-linked with melamine, or an acrylic polyol resin, cross-linked with carbamate-containing melamine. 20 The composition of claim 22, wherein the resin is a thermosetting acrylic melamine resin or an urethane acrylic resin. 2k. The composition of claim 16, wherein the organic 23 material b) is a recording material. 25. The use of a benzotriazole compound of the formula A. B, C or D according to claim 1 in an amount of 0.01 to 5% by weight, based on solid resin particles, for the stabilization of a lacquer composition, which composition resin selected from the group of a thermosetting acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane-modified acrylic melamine, an acrylic resin with carbamate side groups cross-linked with melamine, or an acrylic polyol resin cross-linked melamine containing carbamate groups. 26. Material stabilized with a composition according to any one of the preceding claims. 1 0 7 47 0